Soluble trisazo dyestuffs containing a 2-phenyl-benzimidazolyl, -benzoxazolyl or -benzthiazolyl middle component

ABSTRACT

A water soluble trisazo dyestuff of the formula B 1  --N═N--Z-N═N-M-N═N-B 2  is useful for dyeing substances containing nitrogen or hydroxyl wherein M is ##STR1## B 1  and B 2  are the same or different and are selected from the group consisting of ##STR2## 2,4-dihydroxy-3-quinolyl and 2,6-diamino-5-pyridyl; Z is ##STR3## X is  --O-- or --S--; R 1  is hydrogen, alkyl having 1 to 4 carbon atoms, phenyl or benzyl; R 3  is hydrogen, chloro or alkyl or alkoxy having 1 to 4 carbon atoms; 
     R 4  is hydrogen chloro, alkyl or alkoxy having 1 to 4 carbon atoms, hydroxy, alkanoylamino having 1 to 4 carbon atoms, benzoylamino, naphthoylamino, oxalylamino, carboxyalkylamino having 2 to 5 carbon atoms, sulphoalkylamino having 1 to 4 carbon atoms or oxyalkylamino having 1 to 4 carbon atoms; 
     R 5  is hydrogen or alkyl having 1 to 8 carbon atoms; R 6  is --CN, --COOH, --CONH 2  or --SO 3  H; R 7  is hydrogen, or alkyl having 1 to 4 carbon atoms, R 8  is hydrogen phenyl or phenyl substituted with a methyl, nitro, chloro or sulpho; R 9  is methyl, carboxyl or alkoxycarbonyl having 2 to 5 carbon atoms; R 10  is hydrogen, methyl, methoxy, chloro, --COOH or --SO 3  H; 
     E is a hydroxyl, amino, alkylamino having 1 to 4 carbon atoms, phenylamino, naphthylamino, benzoylamino, naphthoylamino, alkanoylamino having 2 to 5 carbon atoms, carboxyalkylamino having 2 to 5 carbon atoms, sulphoalkylamino having 1 to 4 carbon atoms, hydroxyalkylamino having 1 to 4 carbon atoms dialkylamino having 1 to 4 carbon atoms in each alkyl; 
     E&#39; is hydrogen or the same or a different member of the group of substituents standing for E; 
     R 11 , r 12  and R 13  are alkyl or alkoxy having 1 to 4 carbon atoms, carboxyl, sulpho, chloro, bromo, nitro or methoxycarbonyl; R 14  and R 15  are hydrogen, methyl, ethyl, methoxy, ethoxy or chloro; with the proviso that at least one of M, B 1  and B 2  includes a sulpho substituent.

The present invention relates to a water soluble trisazo dyestuff of theformula B₁ -N═N-Z-N═N-M-N═N-B₂ wherein M is ##STR4## B₁ and B₂ are thesame or different and are selected from the group consisting of ##STR5##2,4-dihydroxy-3-quinolyl and 2,6-diamino-5-pyridyl; Z is ##STR6## X is##STR7## --O-- or --S--; R₁ is hydrogen, alkyl having 1 to 4 carbonatoms, phenyl or benzyl; R₃ is hydrogen, chloro or alkyl or alkoxyhaving 1 to 4 carbon atoms;

R₄ is hydrogen chloro, alkyl or alkoxy having 1 to 4 carbon atoms,hydroxy, alkanoylamino having 1 to 4 carbon atoms, benzoylamino,naphthoylamino, oxalylamino, carboxyalkylamino having 2 to 5 carbonatoms, sulphoalkylamino having 1 to 4 carbon atoms or oxyalkylaminohaving 1 to 4 carbon atoms;

R₅ is hydrogen or alkyl having 1 to 8 carbon atoms; R₆ is --CN, --COOH,--CONH₂ or --SO₃ H; R₇ is hydrogen or alkyl having 1 to 4 carbon atoms;R₈ is hydrogen, phenyl or phenyl substituted with a methyl, nitro,chloro or sulpho; R₉ is methyl, carboxyl or alkoxycarbonyl having 2 to 5carbon atoms; R₁₀ is hydrogen, methyl, methoxy, chloro, --COOH or --SO₃H;

E is a hydroxyl, amino, alkylamino having 1 to 4 carbon atoms,phenylamino, naphthylamino, benzoylamino, naphthoylamino, alkanoylaminohaving 2 to 5 carbon atoms, carboxyalkylamino having 2 to 5 carbonatoms, sulphoalkylamino having 1 to 4 carbon atoms, hydroxyalkylaminohaving 1 to 4 carbon atoms dialkylamino having 1 to 4 carbon atoms ineach alkyl;

E' is hydrogen or the same or a different member of the group ofsubstituents standing for E.

R₁₁, R₁₂ and R₁₃ are alkyl or alkoxy having 1 to 4 carbon atoms,carboxyl, sulpho, chloro, bromo, nitro or methoxycarbonyl; R₁₄ and R₁₅are hydrogen, methyl, ethyl, methoxy, ethoxy, or chloro; with theproviso that at least one of M, B₁ and B₂ includes a sulpho substituent.The dyestuff of the present invention is useful for dyeing or printingnatural or synthetic material which contains nitrogen or hydroxyl. Thedyestuff may be in the form of alkali metal, alkaline earth metal orammonium salts of the carboxyl or sulpho groups.

One preferred embodiment of the water soluble dyestuff of the presentinvention is wherein at least one of B₁ and B₂ is ##STR8##

Another preferred embodiment of the water soluble trisazo dyestuff iswherein B₁, B₂ or both is ##STR9##

Another preferred embodiment of the water soluble trisazo dyestuff iswherein B₁, B₂ or both is ##STR10##

Another preferred embodiment of the water soluble trisazo dyestuff iswherein B₁, B₂ or both is ##STR11##

Another preferred embodiment of the water soluble trisazo dyestuff iswherein B₁, B₂ or both is ##STR12##

The divalent radicals M of the formula IV are derived from couplingcomponents of the formula V

    m - nh.sub.2                                               v

of the aromatic series which contain a diazotisable amino group andwhich can additionally carry other substituents which are customary indyestuff chemistry.

In particular, the radicals M are derived from diazotisable couplingcomponents M-NH₂ (V) of the aminobenzene series of the formula Vc##STR13##

In preferred diazotisable coupling components of the aminobenzene seriesof the formula Vc, the substituent R₃ represents H, chlorine, alkylhaving 1-2 C atoms, or alkoxy having 1-2 C atoms and the substituent R₄represents H, chlorine, alkyl having 1-2 C atoms, hydroxyl, alkoxyhaving 1-2 C atoms, acylamino having 1-2 C atoms in the acyl radical,benzoylamino, oxalylamino or carboxyalkylamino, sulphoalkylamino oroxyalkylamino having in each case 1-2 C atoms in the alkyl radical.

The radicals B₁ and B₂ of a coupling component which are present in thedyestuffs according to the invention can be derived from the benzene,naphthalene, 6-hydroxy-2-pyridone, pyrazolone, acetoacetic acidarylamide, dihydroxyquinoline or 2,6-diaminopyridine series.

If the coupling components B₁ and/or B₂ are derived from the benzene ornaphthalene series, B₁ and/or B₂ denote a phenyl radical or anα-naphthyl or β-naphthyl radical which is monosubstituted ordisubstituted by amino and/or hydroxyl, and amino groups can also bemonosubstituted or disubstituted by alkyl having 1∝4 C atoms ormonosubstituted by aryl or aroyl having 6-12 C atoms, acyl having 2-5 C.atoms, carboxyalkyl or sulphoalkyl or hydroxyalkyl, in each case havingespecially 1 or 2 C atoms in the alkyl radical, or disubstituted by arylhaving 6-12 C atoms or acyl having 2-5 C atoms and alkyl having 1-Catoms, and the phenyl or naphthyl radical can, in addition, also bemonosubstituted or disubstituted by alkyl having 1-4 C atoms, alkoxyhaving 1-4 C atoms, carboxyl, sulpho, chlorine, bromine, nitro oralkoxycarbonyl having 1-C. atoms in the alkoxy radical. In a preferredgroup of dyestuffs according to the invention, B₁ and/or B.sub. 2represent a phenyl radical which is monosubstituted or disubstituted byamino and/or hydroxyl, it being possible for amino groups to carry asulphoethyl, sulphomethyl, carboxymethyl, carboxyethyl, hydroxymethyl,hydroxyethyl, acetyl, benzoyl, phenyl or tolyl substituent or one or twomethyl or ethyl substituents and for the phenyl radical, in addition, tobe monosubstituted by alkyl having 1-2 C atoms, alkoxy having 1-2 Catoms, carboxyl, sulpho, chlorine or nitro. A further preferred group ofdyestuffs according to the invention contains, for B₁ and/or B₂, anα-naphthyl or β-naphthyl radical which is monosubstituted ordisubstituted by amino and/or hydroxyl, it being possible for aminogroups to carry a sulphoethyl, sulphomethyl, carboxymethyl,carboxyethyl, hydroxymethyl, hydroxyethyl, acetyl, benzoyl, phenyl ortolyl substituent or one or two methyl or ethyl substituents and for thenaphthyl radical, in addition, to be monosubstituted by sulpho, carboxylor chlorine or disubstituted by --SO₃ H.

If the coupling components B₁ and/or B₂ which are present in thedyestuffs according to the invention are derived from the6-hydroxypyridone series, preferred dyestuffs are those in which B₁and/or B₂ is a radical of the formula VI ##STR14## wherein R₅ denotes Hor alkyl having 1-8 C atoms, R₆ denotes CN, COOH, --CONH₂ or --SO₃ H andR₇ denotes H or alkyl having 1-4 C atoms.

The dyestuffs according to the invention in which B₁ and/or B₂ is aradical of the abovementioned formula wherein R₅ denotes hydrogen ormethyl and R₆ denotes --CN or --SO₃ H, are particularly valuable in thisseries.

If the radicals of the coupling components B₁ and/or B₂ in the dyestuffsaccording to the invention are derived from the pyrazolone series, theyhave the formula VII ##STR15## wherein R₈ denotes hydrogen or a phenylradical which is optionally monosubstituted or disubstituted by methyl,nitro, chlorine and/or sulpho, and R₉ denotes a methyl group, a carboxylgroup or an alkoxycarbonyl group having 2-5 C atoms.

If the radicals B₁ and/or B₂ of the coupling component in the dyestuffsaccording to the invention are derived from the series of theacetoacetoarylamides, they correspond to the formula VIII ##STR16## orto a tautomeric form thereof wherein the phenyl nucleus can, inaddition, be monosubstituted or disubstituted by methyl, methoxy,chlorine, --COOH or --SO₃ H and, in addition, can have a methyl ormethoxy group as a third substituent.

The radical of a coupling component B₁ and/or B₂ in the dyestuffsaccording to the invention can also be a 2,4-dihydroxy-3-quinolyl or2,6-diamino-5-pyridyl radical.

The divalent radical of 2-phenylbenzimidazole, 2-phenylbenzoxazole or2-phenylbenzthiazole which is present as the middle component in thedyestuffs according to the invention can be linked, via the azo bridge,to the coupling component B₁ either by means of the non-fused 2-phenylnucleus (nucleus I) or by means of the fused phenyl nucleus (nucleusII).

Accordingly, mixtures of dyestuffs which are isomeric with one anotherin respect of the incorporation of the heterocyclic middle component arealso to be regarded as dyestuffs according to the invention within themeaning of the present invention.

The azo bridge which is linked to the nucleus II of the benzimidazole,benzoxazole or benzthiazole system can be in the 5-position or the6-position, which is intended to be indicated in the general formula bythe bond line between the 5- and 6-positions.

The nuclei I and II of the heterocyclic middle component can besubstituted by one or two identical or different substituents of thegroup alkyl and/or alkoxy, having in each case 1 or 2 C atoms, and/orhalogen. Preferred dyestuffs according to the invention are those inwhich the nuclei I and/or II are substituted by a methyl group orchlorine. Dyestuffs according to the invention which are particularlypreferred are those in which the heterocyclic middle component is adivalent radical of 2-phenylbenzimidazole.

The dyestuffs according to the invention are present, in particular, inthe form of their sodium salts. Dyestuffs which contain 2-4 acid groupsare particularly valuable. Acid groups in this sense are the carboxylgroup and the sulphonic acid group, which are capable of forming salts.

The dyestuffs according to the invention, of the general formula I

    b.sub.1 -n═n-z-n═n-m-n═n-b.sub.2               i

wherein Z denotes the radical ##STR17## and B₁, B₂, X and M have theabovementioned meanings, can be manufactured by diazotising adiazotisable disazo dyestuff of the formula IX

    b.sub.1 -n═n-z-n═n-m-nh.sub.2                      ix

and coupling the product with a coupling component of the formula X

    b.sub.2 -h                                                 x

the diazotised disazo dyestuff IX is coupled with the coupling componentX in a manner which is in itself known, in an aqueous medium which canalso contain water-miscible organic solvents, for example methanol orethanol, and known coupling accelerators, such as urea, pyridine orthiourea, at temperatures of -10° to +30° C., preferably 0°-20° C., andwithin a pH range of 4 to 12, preferably 7 to 10.

The diazotisable disazo dyestuff of the formula IX which is required canbe obtained by tetrazotising a heterocyclic diamine of the formula XI##STR18## and coupling the product on one side with a coupling componentof the formula XII

    b.sub.1 -h                                                 xii

to give the diazotised monoazo dyestuff of the formula XIII

    b.sub.1 -n═n-z-n═n.sup.⊕ ]y.sup.⊖      XIII

wherein y.sup.⊖ represents an anion, preferably the anion of a mineralacid, for example hydrochloric acid or sulphuric acid.

The diazotised monoazo dyestuff XIII obtained in this way is thencombined with a diazotisable coupling component of the formula V

    m-nh.sub.2                                                 v

to give the disazo dyestuff IX.

Diazotisable disazo dyestuffs of the formula IX which are suitable forthe manufacture of the dyestuffs, according to the invention, of theformula I can, furthermore, also be manufactured by tetrazotisingheterocyclic diamines of the general formula XI and first coupling theproduct on one side with a diazotisable coupling component of theformula V

    m-nh.sub.2                                                 v

to give the diazotised monoazo dyestuff of the formula XIV

    y.sup.⊖ [.sup.⊕ N═N-Z-N═N-M-NH.sub.2   XIV

wherein y.sup.⊖, Z and M-NH₂ have the meaning already mentioned.

The diazotised monoazo dyestuff XIV is then combined with the couplingcomponent B₁ -H (XII), the required diazotisable disazo dyestuff of theformula IX being obtained. The heterocyclic diamine XI is tetrazotisedin a manner which is in itself known, for example by the action ofnitrous acid in an acid, aqueous medium at temperatures of -10° to +30°C. The subsequent coupling on one side with the coupling component B₁ -H(XII) to give the diazotised monoazo dyestuff XIII or with thediazotisable coupling component M-NH₂ (V) to give the diazotised monoazodyestuff XIV is carried out in an aqueous medium at temperatures of -10°to +30° C. and at pH values of 3 to 12, preferably 4 to 9.

Water-miscible solvents, for example alcohols, can, if appropriate, bepresent in the aqueous medium. Coupling accelerators which are inthemselves known, for example pyridine, urea or thiourea, can be presentin the coupling reactions.

The new trisazo dyestuffs of the general formula I can, furthermore,also be manufactured by tetrazotising a heterocyclic diamine of theformula XI and coupling the product, in the manner already described,with a diazotisable coupling component of the formula V

    m-nh.sub.2                                                 v

to give the diazotised monoazo dyestuff of the general formula XIV

    y.sup.⊖ [.sup.⊕ N═N-Z-NP═N-M-NH.sub.2  XIV

wherein y.sup.⊖, Z and M-NH₂ have the meaning already mentioned.

The diazotisable amino group in the radical M-NH₂, of the diazotisedmonoazo dyestuff XIV is then diazotised further and the resultingtetrazotised monoazo dyestuff of the general formula XV

    [.sup.⊕ n═n-z-n═n-m-n═n.sup.⊕ ]2 y.sup.⊖XV

is coupled with 1 mol of each of the coupling components of the formulaeB₁ -H (XII) and B₂ -H (X), wherein B₁ and B₂ are the same or differentand have the same meaning as defined above to give the trisazo dyestuff,according to the invention, of the formula I.

This process makes it possible, by employing two different couplingcomponents B₁ H and B₂ H, to obtain mixtures of dyestuffs according tothe invention which differ in respect of the radicals represented by B₁and B₂. If, for example, two special coupling components B₁ H and B₂ Hare reacted simultaneously with a tetrazo compound XV, mixtures ofdyestuffs according to the invention of the general formulae

    B.sub.1 -N═N-Z-N═N-M-N═N-B.sub.1

    b.sub.2 -n═n-z-n═n-m-n═n-b.sub.2

    b.sub.1 -n═n-z-n═n-m-n═n-b.sub.2 and

    B.sub.2 -N═N-Z-N═N-M-N═N-B.sub.1

can be obtained. Such mixtures of dyestuffs according to the inventionalso form part of the subject of the invention and have a hightechnological value.

Valuable mixtures of the dyestuffs of the present invention are alsoobtained if mixtures of several, preferably two, different couplingscomponents coming within the above-stated definition are used for B₁ -Hand/or B₂ H.

In this manufacturing process, the heterocyclic diamine of the formulaXI is also tetrazotised in a manner which is in itself known, forexample as indicated above.

The subsequent one-sided coupling with the diazotisable couplingcomponent of the formula M-NH₂ (V) is carried out in an aqueous mediumat pH values of 3 to 12, preferably 4 to 9. The further diazotisation ofthe diazotised monoazo dyestuff XIV to give the tetrazotised monoazodyestuff XV is also carried out in an aqueous medium at pH 0-3, whilethe coupling of XV with two identical or different mols of B₁ H (XII) orB₂ -H (X) to give the final dyestuff I is carried out at pH valuesbetween 4 and 12, preferably 7 to 10.

The following are examples of heterocyclic diamines of the formula XI##STR19## which are suitable for the manufacture of the trisazodyestuffs, according to the invention, of the general formula I:2-(4'-aminophenyl)-5- (or 6)-amino-benzimidazole,1-methyl-2-(4'-aminophenyl)-6-amino-benzimidazole,1-methyl-2-(4'-aminophenyl)-5-amino-benzimidazole,1-ethyl-2-(4'-aminophenyl)-5-amino-benzimidazole,1-propyl-2-(4'-aminophenyl)-5-amino-benzimidazole,1-butyl-2-(4'-aminophenyl)-5-amino-benzimidazole,1-phenyl-2-(4'-aminophenyl)-5-amino-benzimidazole,1-benzyl-2-(4'-aminophenyl)-5-amino-benzimidazole,2-(4'-aminophenyl)-4-methyl-5-amino-benzimidazole, (identical with2-(4'-aminophenyl)-6-amino-7-methyl-benzimidazole),2-(4'-aminophenyl)-5-amino-6-methyl-benzimidazole (identical with2-(4'-aminophenyl)-5-methyl-6-amino-benzimidazole),2-(4'-aminophenyl)-5-amino-6-chloro-benzimidazole (identical with2-(4'-aminophenyl)-5-chloro-6-amino-benzimidazole),2-(4'-aminophenyl)-5-amino-7-chloro-benzimidazole (identical with2-(4'-aminophenyl)-4-chloro-6-amino-benzimidazole),2-(4'-aminophenyl)-5-amino-6 -ethoxy-benzimidazole) (identical with2-(4'-aminophenyl)-5-ethoxy-6-amino-benzimidazole),2-(2'-methyl-4'-aminophenyl)-5- (or 6)-amino-benzimidazole,2-(3'-methyl-4'-aminophenyl)-5- (or 6)-amino-benzimidazole,2-(2'-chloro-4'-aminophenyl)-5- (or 6)-amino-benzimidazole,2-(3'-chloro-4'-aminophenyl)-5- (or 6)-amino-benzimidazole,2-(4'-aminophenyl)-5-amino-benzoxazole,2-(4'-aminophenyl)-6-amino-benzoxazole,2-(4'-amino-2'-chloro-phenyl)-5-amino-benzoxazole,2-(4'-aminophenyl)-4-methyl-5-amino-benzoxazole,2-(4'-aminophenyl)-5-amino-benzthiazole,2-(4'-aminophenyl)-6-amino-benzthiazole,2-(4'-aminophenyl)-6-methyl-5-amino-benzthiazole,2-(4'-aminophenyl)-5-methyl-6-amino-benzthiazole and2-(4'-aminophenyl)-5-chloro-6-amino-benzthiazole.

Tautomerism is possible in the case of the benzimidazoles having X ═--NH--, so that, for example, it is not possible to distinguish betweenthe 5-position and the 6-position. If further substituents areadditionally present in the nucleus II, two different possible methodsof numbering result, and this has been taken into consideration in theabove text.

Furthermore, all the heterocyclic diamines which can be obtained inaccordance with the manufacturing methods indicated in U.S. Pat. No.4,033,945, column 4, line 35 through column 7, line 25, are suitable forthe manufacture of trisazo dyestuffs according to the invention.

The heterocyclic diamines XI have an unsymmetrical structure. When atetrazotised, heterocyclic diamine XI is coupled with a couplingcomponent B₁ -H (XII) or with a diazotisable coupling component M-NH₂(V), two possibilities can arise, depending on which side of thetetrazotised, heterocyclic diamine couples first. In conformity withthese possibilities, the following two structures are given for thefinal dyestuffs: ##STR20##

It can be assumed that the trisazo dyestuffs (I) which can bemanufactured in the said manner represent mixtures of the two components(Ia) and (Ib). The following are examples of suitable diazotisablecoupling components of the formula M-NH₂ (V): 3-methylaniline,2,5-dimethylaniline, 2,5-dimethoxyaniline, 2-methoxy-5-methylaniline,2-ethoxy-5-methylaniline, 3-aminophenol, 3-methoxyaniline,3-aminoformanilide, 1-amino-3-acetylaminobenzene,1-amino-3-acetylamino-6-methylbenzene,1-amino-3-acetylamino-6-ethylbenzene, 1-amino-3-benzoylamino-benzene,1-amino-3-propionylamino-benzene, 1-amino-3-butyrylamino-benzene,1-amino-3-oxalylaminobenzene, 1-amino-3-oxalylamino-6-methylbenzene,1-amino-3-acetylamino-6-methoxybenzene,1-amino-3-acetylamino-6-ethoxybenzene,1-amino-3-carboxymethylaminobenzene,1-amino-3-carboxymethylamino-6-methylbenzene,1-amino-3-carboxyethylaminobenzene, 1-amino-3-oxyethylaminobenzene,1-amino-3-sulphomethylaminobenzene and1-amino-3-sulphoethylaminobenzene.

In the manufacture of the dyestuffs I according to the invention, thediazotisable coupling components M-NH₂ (V), in particular the couplingcomponents of the aminobenzene series of the formula Vc, can also beemployed in the form of their arylamino-methanesulphonic acids, whichcan be manufactured by reaction with formaldehyde and sodium bisulphite,or in the form of their arylaminosulphuric acids, which can be obtainedby reaction with halogenosulphonic acids (compare Houben-Weyl, "Methodender Organischen Chemie" ("Methods of Organic Chemistry"), volume X/3(1965), pages 241-243. The coupling product can subsequently beconverted by acid or alkaline hydrolysis into the diazotisable disazodyestuff having a free amino group of the formula IX. The following areexamples of coupling components of the aminobenzene series of theformula (Vc) which are preferably employed in the form of theirarylamino-methanesulphonic acids, which can be manufactured by reactionwith formaldehyde and sodium bisulphite, or in the form of theirarylaminosulphuric acids, which can be obtained by reaction withhalogenosulphonic acids: aniline, 2-aminotoluene, 3-aminotoluene,2-amino-1-ethylbenzene, 3-amino-1-ethylbenzene, 2-methoxyaniline,2-ethoxyaniline, 3-methoxyaniline, 3-ethoxyaniline, 2-chloroaniline and3-chloroaniline.

The following are examples of coupling components of the formula B₁ -H(XII) and/or B₂ -H (X) which are suitable for the manufacture of thedyestuffs according to the invention: phenol, 2-methylphenol,4-methylphenol, 3-chlorophenol, 3-methoxyphenol,2-hydroxybenzenesulphonic acid, 3-hydroxybenzenesulphonic acid,1,3-dihydroxybenzene, 1,3-dihydroxy-2-chlorobenzene,1,3-dihydroxy-4-chlorobenzene, 1,3-dihydroxy-5-methylbenzene,1,3-dihydroxy-4-hexylbenzene, 1,3-dihydroxybenzene-4-sulphonic acid,1,3-dihydroxybenzene-5-sulphonic acid, 1-amino-3-hydroxybenzene,1-amino-3-hydroxy-4-chlorobenzene, 1-(phenylamino)-3-hydroxybenzene,1-(2'-methyl-phenylamino)-3-hydroxybenzene, 3-aminophenol-4-sulphonicacid, 3-aminophenol-6-sulphonic acid, 1,3-diaminobenzene,1,3-diamino-4-methylbenzene, 1,3-diamino-4-ethylbenzene,1,3-diamino-4-n-propylbenzene, 1,3-diamino-4-n-butylbenzene,1,3-diamino-4-chlorobenzene, 1,3-diamino-4-bromobenzene,1,3-diamino-4-methoxybenzene, 1,3-diamino-4-Ethoxybenzene,1,3-diamino-4-nitrobenzene, 1-amino-3-dimethylaminobenzene,1,3-diamino-4-n-propoxybenzene, 1,3-diamino-4-isopropoxybenzene,1-amino-3-diethylaminobenzene, 1-acetylamino-3-diethylaminobenzene,1-amino-3-carboxymethylaminobenzene, 1-amino-3-carboxyethylaminobenzene,1-amino-3-sulphomethylaminobenzene, 1-amino-3-oxyethylaminobenzene,1-amino-3-sulphoethylamino-benzene, 1,3-diaminobenzene-4-sulphonic acid,2-hydroxybenzoic acid, 5-chloro-2-hydroxybenzoic acid,2-hydroxy-3-methyl-benzoic acid, 2-hydroxy-4-methyl-benzoic acid,2-hydroxy-5-sulpho-benzoic acid, 2-hydroxybenzoic acid ethyl ester,1-hydroxynaphthalene, 1,6-dihydroxynaphthalene,1-hydroxynaphthalene-3-sulphonic acid, 1-hydroxynaphthalene-4-sulphonicacid, 1-hydroxynaphthalene-3,6-disulphonic acid,1-hydroxynaphthalene-5-, -6- and -7-sulphonic acid,2-hydroxynaphthalene, 2-hydroxynaphthalene-3-carboxylic acid,2-hydroxynaphthalene-6-, -7- and -8-sulphonic acid,2-hydroxynaphthalene-3,6-disulphonic acid,2-hydroxynaphthalene-6,8-disulphonic acid, 1-aminonaphthalene,1-aminonaphthalene-4-, -5-, -6- and -7-sulphonic acid,1-carboxymethylamino-naphthalene-6-sulphonic acid,1-carboxymethylamino-naphthalene-7-sulphonic acid,1-hydroxyethylamino-naphthalene-6-sulphonic acid,1-hydroxyethylaminonaphthalene-7-sulphonic acid,1-phenylamino-naphthalene-8-sulphonic acid,1-aminonaphthalene-3,6-disulphonic acid,1-aminonaphthalene-5,7-disulphonic acid,1-aminonaphthalene-3,7-disulphonic acid, 2-aminonaphthalene-5-sulphonicacid, 2-aminonaphthalene-6-sulphonic acid,2-aminonaphthalene-7-sulphonic acid, 2-aminonaphthalene-8-sulphonicacid, 2-aminonaphthalene-3,6-disulphonic acid,2-aminonaphthalene-4,8-disulphonic acid,2-aminonaphthalene-6,8-disulphonic acid,2-aminonaphthalene-5,7-disulphonic acid, 1-amino-7-hydroxynaphthalene,2-amino-7-hydroxynaphthalene, 1-amino-5-hydroxynaphthalene-7-sulphonicacid, 1-amino-7-hydroxynaphthalene-5-sulphonic acid,1-amino-8-hydroxynaphthalene-4-sulphonic acid,1-amino-8-hydroxynaphthalene-2,4-disulphonic acid,1-amino-8-hydroxynaphthalene-3,6-disulphonic acid,1-amino-8-hydroxynaphthalene-4,6-disulphonic acid,2-amino-5-hydroxy-naphthalene-7-sulphonic acid,2-amino-8-hydroxynaphthalene-6-sulphonic acid,2-amino-8-hydroxynaphthalene-3,6-disulphonic acid,2-phenylamino-8-hydroxynaphthalene-6-sulphonic acid,2-phenylamino-5-hydroxynaphthalene-7-sulphonic acid,2-carboxymethylamino-5-hydroxynaphthalene-7-sulphonic acid,2-benzoylamino-5-hydroxynaphthalene-7-sulphonic acid,2-acetylamino-5-hydroxynaphthalene-7-sulphonic acid,1-acetylamino-8-hydroxynaphthalene-3,6-disulphonic acid,1-benzoylamino-8-hydroxynaphthalene-3,6-disulphonic acid,2-acetylamino-8-hydroxynaphthalene-6-sulphonic acid,2-carboxymethylamino-8-hydroxynaphthalene-6-sulphonic acid,2-methylamino-8-hydroxynaphthalene-6-sulphonic acid,2-dimethylamino-8-hydroxynaphthalene-6-sulphonic acid,2-oxyethylamino-8-hydroxynaphthalene-6-sulphonic acid, acetoacetic acidanilide, acetoacetic acid-o-, -m- and -p-toluidide, acetoaceticacid-2-sulphoanilide, acetoacetic acid-3-sulphoanilide, acetoaceticacid-4-sulphoanilide, acetoacetic acid-4-carboxyanilide, acetoaceticacid-2-methoxyanilide, acetoacetic acid-4-methoxyanilide, acetoaceticacid-2-methyl-4-chloroanilide, acetoacetic acid-2-chloroanilide,acetoacetic acid-4-chloroanilide, acetoaceticacid-2,5-dimethoxy-4-chloroanilide, 3-methyl-5-pyrazolone, 1-phenyl-3-methyl-5-pyrazolone, 1-(2'-sulphophenyl)-3-methyl-5-pyrazolone,1-(3'-sulphophenyl)-3-methyl-5-pyrazolone,1-(4'-sulphophenyl)-3-methyl-5-pyrazolone,1-phenyl-5-pyrazolone-3-carboxylic acid,1-(4'-sulphophenyl)-5-pyrazolone-3-carboxylic acid,1-(3'-nitro-phenyl)-3-methyl-5-pyrazolone,1-(4'-methyl-phenyl)-3-methyl-5-pyrazolone,1-(4'-methyl-phenyl)-3-butoxycarbonyl-5-pyrazolone,1-(2',5'-dichloro-4'-sulphophenyl)-3-methyl-5-pyrazolone,1-(3'-sulpho-phenyl)-3-ethoxycarbonyl-5-pyrazolone, 1-(6'-chloro-3'-sulpho-phenyl)-3-methyl-5-pyrazolone,1-(2'-chloro-4'-sulpho-phenyl)-3-methyl-5-pyrazolone,1-(4'-sulpho-2'-methylphenyl)-3-methyl-5-pyrazolone,3-cyano-6-hydroxy-2-pyridone, 4-methyl-3-cyano-6-hydroxy-2-pyridone,4-methyl-3-carboxy-6-hydroxy-2-pyridone,4-methyl-6-hydroxy-2-pyridone-3-carboxylic acid amide,1,4-dimethyl-3-cyano-6-hydroxy-2-pyridone,1-(n)-butyl-3-cyano-4-methyl-6-hydroxy-2-pyridone,1-(2-ethylhexyl)-3-cyano-4-methyl-6-hydroxy-2-pyridone,1-ethyl-3-cyano-4-butyl-6-hydroxy-2-pyridone,1-ethyl-3-carboxy-4-methyl-6-hydroxy-2-pyridone,1-ethyl-3-sulpho-4-methyl-6-hydroxy-2-pyridone,1,4-dimethyl-3-sulpho-6-hydroxy-2-pyridone,4-methyl-3-sulpho-6-hydroxy-2-pyridone,1-isopropyl-3-amidocarbonyl-4-methyl-6-hydroxy-2-pyridone,2,4-dihydroxyquinoline and 2,6-diamino-3-cyano-4-methylpyridine.

The trisazo dyestuffs according to the invention have a high tinctorialstrength. They are outstandingly suitable as direct dyestuffs for dyeingand printing natural or synthetic fibre materials which contain hydroxylgroups or which contain nitrogen, especially cotton and regeneratedcellulose as well as wool, wool/cotton union, silk, polyamide, leatherand paper. Dyeing and printing are carried out by the customaryprocesses. Orange, brown, red, blue, green and black dyeings of goodfastness properties are obtained on the said substrates.

The new dyestuffs are especially distinguished by good fastness to wetprocessing, for example fastness to water, washing at 40° C. and washingat 60° C., and by good fastness to perspiration (alkaline and acid) andfastness to acids.

If X is ##STR21## especially ##STR22## the new dyestuffs are absorbedparticularly exhaustively onto the fibre materials to be dyed, whendyeing by the exhaustion process, so that a nearly clear residual liquoris obtained.

The new dyestuffs are particularly suitable for dyeing fibers composedof cotton and regenerated cellulose and for dyeing polyamide, leatherand paper.

In the examples which follow, parts denote parts by weight, percentagesdenote percentages by weight and the temperatures are quoted in degreescentigrade.

EXAMPLE 1

22.4 parts of 2-[4'-aminophenyl]-5 (or 6)-amino benzimidazole in amixture of 200 parts of water and 50 parts of 30% strength aqueoushydrochloric acid are tetrazotised with a solution of 13.8 parts ofsodium nitrite in 50 parts of water, while adding ice, at 0°-5° C. Afterthe sodium nitrite solution has been added, stirring is continued for 1hour at 0°-5° C. and excess nitrous acid is removed with amidosulphonicacid. A solution of 15.6 parts of 2-hydroxybenzoic acid and 40 parts ofsodium carbonate in 150 parts of water are then added rapidly to theyellow solution of the tetrazo component. The one-sided coupling iscomplete after stirring for 2-3 hours at pH 8-10. The suspension of thediazotised monoazo dyestuff is then adjusted to pH 3 with 80 parts of30% strength hydrochloric acid and a solution of 12.1 parts of2,5-dimethylaniline in 100 parts of water and 10 parts of 30% strengthhydrochloric acid is then added. The pH value of the coupling mixture israised to 4.5-5 by adding a solution of 14 parts of sodium acetate in100 parts of water. Stirring is continued for 12 hours at 5°-10° C. inorder to complete the coupling.

The suspension of the brown disazo dyestuff is then adjusted to pH 1-2with 45 parts of 30% strength hydrochloric acid and is diazotisedfurther at 0°-5° C. with a solution of 7.6 parts of sodium nitrite in 30parts of water. After stirring for a further 2 hours, excess nitrousacid is removed with amidosulphonic acid and the suspension of the diazocomponent obtained in this way is then run into a solution of 23.9 partsof 2-amino-8-hydroxynaphthalene-6-sulphonic acid, 4 parts of sodiumhydroxide and 50 parts of sodium carbonate in 250 parts of water. Thedyestuff of the structure ##STR23## which separates out at pH 7.5 isfiltered off and dried.

A solution of 0.2 part of sodium carbonate and 4 parts of sodiumsulphate decahydrate in 200 parts of water is made up at 40° C. in a dyebeaker which is placed in a bath which can be heated.

0.2 part of the dyestuff which has been prepared is then added. 10 g ofa cotton fabric are kept continuously agitated in the ready-to-use dyeliquor, the temperature is raised to 95° C. and dyeing is carried outfor a further 45 minutes at this temperature. The dyed cotton fabric isthen withdrawn from the residual liquor which retains ony a slightcoloration and the liquor still adhering is removed by wringing-out. Thedyed material is then rinsed with cold water and dried at 60° C.

A brown dyeing with a good depth of colour and with good fastnessproperties, especially good fastness to washing, water and perspiration,is obtained.

Brown trisazo dyestuffs which are distinguished by a high tinctorialstrength and by good fastness properties, especially by good fastness towashing, water and perspiration, are also obtained if2-hydroxy-3-methyl-benzoic acid is employed instead of 2-hydroxybenzoicacid or if the diazotisable coupling component 3-methylaniline,3-methoxyaniline, 2-methoxy-5-methylaniline, 2-methoxy-5-chloroaniline,2-ethoxy-5-methylaniline, 2,5-dimethoxyaniline, 1-amino-3-formanilide,1-amino-3-acetylaminobenzene, 1-amino-3-acetylamino-6-methylbenzene,1-amino-3-oxalylaminobenzene, 1-amino-3-oxalylamino-6-methylbenzene,1-amino-3-acetylamino-6-methoxybenzene,1-amino-3-acetylamino-6-ethoxybenzene or 3-aminophenol are employedinstead of 2,5-dimethylaniline or if the coupling component2-methylamino-8-hydroxynaphthalene-6-sulphonic acid,2-dimethylamino-8-hydroxynaphthalene-6-sulphonic acid,2-phenylamino-8-hydroxynaphthalene-6-sulphonic acid,2-acetylamino-8-hydroxynaphthalene-6-sulphonic acid,2-carboxymethylamino-8-hydroxynaphthalene-6-sulphonic acid,2-carboxyethylamino-8-hydroxynaphthalene-6-sulphonic acid,2-hydroxyethylamino-8-hydroxynaphthalene-6-sulphonic acid,2-amino-8-hydroxynaphthalene-3,6-disulphonic acid, 2-amino-5-hydroxynaphthalene-7-sulphonic acid,2-acetylamino-5-hydroxynaphthalene-7-sulphonic acid,2-carboxymethylamino-5-hydroxynaphthalene-7-sulphonic acid,2-sulphomethylamino-8-hydroxynaphthalene-6-sulphonic acid,2-hydroxyethylamino-5-hydroxynaphthalene-7-sulphonic acid or2-sulphomethylamino-5-hydroxynaphthalene-7-sulphonic acid are employedinstead of 2-amino-8-hydroxynaphthalene-6-sulphonic acid.

EXAMPLE 2

22.4 parts of 2-[4'-aminophenyl]-5 (or 6)-amino benzimidazole in amixture of 200 parts of water and 50 parts of 30% strength aqueoushydrochloric acid are tetrazotised with a solution of 13.8 parts ofsodium nitrite in 50 parts of water, while adding ice, at 0°-5° C. Afterthe sodium nitrite solution has been added, stirring is continued forabout 1 hour at 0°-5° C. and the excess nitrous acid is then removedwith amidosulphonic acid. A solution of 13.9 parts of2-methoxy-5-methylaniline in 100 parts of water and 10 parts of 30%strength hydrochloric acid is then run, at 0°-5° C., into the yellowsolution of the tetrazo compound. The pH value is then adjusted to 4.5by sprinkling in 20 parts of sodium acetate and stirring is continuedfor 3 hours in order to complete the one-sided coupling. The pH of themixture of the diazotised monoazo dyestuff is then adjusted to 1.5 with25 parts of 30% strength aqueous hydrochloric acid and a solution of 7.6parts of sodium nitrite in 30 parts of water is added at 0°-5° C.Stirring is continued for two hours in order to complete thediazotisation and excess nitrous acid is removed with amidosulphonicacid. The red-brown solution of the tetrazotised monoazo dyestuff thusobtained is then added at 0°-5° C. to a solution of 65 parts of1-amino-8-hydroxynaphthalene-3,6-disulphonic acid, 8 parts of sodiumhydroxide and 42.5 parts of sodium carbonate in 300 parts of water andstirring is continued for 3 hours at pH 8-9. The dyestuff of thestructure ##STR24## which has separated out with the aid of 100 parts ofsodium chloride at pH 5 is filtered off and dried.

The trisazo dyestuff dyes cotton in a greenish-tinged blue shade. Thedyeings have a good depth of colour and good fastness properties, inparticular very good fastness to washing, water and perspiration.

Blue trisazo dyestuffs which are distinguished by high tinctorialstrength and by good fastness properties, in particular by good fastnessto washing, water and perspiration, are also obtained if thediazotisable coupling components 3-methylaniline, 2,5-dimethylaniline,3-methoxyaniline, 3-aminophenol, 2-methoxy-5-chloroaniline,2-ethoxy-5-methylaniline, 2,5-dimethoxyaniline, 1-amino-3-formanilide,1a-amino-3-acetylaminobenzene, 1-amino-3-acetylamino-6-methylbenzene,1-amino-3-oxalylaminobenzene, 1-amino-3-oxalylamino-6-methylbenzene,1-amino-3-acetylamino-6-methoxybenzene or1-amino-3-actylamino-6-ethoxybenzene are employed instead of2-methoxy-5-methylaniline or if the coupling components1,8-dihydroxynaphthalene-3,6-disulphonic acid,1-amino-8-hydroxynaphthalene-2,4-disulphonic acid,1-amino-8-hydroxynaphthalene-4,6-disulphonic acid,1-amino-8-hydroxynaphthalene-4-sulphonic acid,1-acetylamino-8-hydroxynaphthalene-3,6-disulphonic acid,1-benzoylamino-8-hydroxynaphthalene-3,6-disulphonic acid or2-amino-8-hydroxynaphthalene-3,6-disulphonic acid are employed insteadof 1-amino-8-hydroxynaphthalene-3,6-disulphonic acid.

EXAMPLE 3

The tetrazotisation of 22.4 parts of2-(4'-aminophenyl)-6-aminobenzimidazole, the one-sided coupling of theresulting tetrazo compound with 13.9 parts of 2-methoxy-5-methylanilineand the further diazotisation of the diazotised monoazo dyestuff to givethe tetrazotised monoazo dyestuff of the formula ##STR25## is carriedout according to the instructions of Example 2.

The solution of the tetrazotised monoazo dyestuff thus prepared is thenrun, at 0°-5° C., into a solution of 51.6 parts of1-(4'-sulphophenyl)-3-methyl-5-pyrazolone, 8 parts of sodium hydroxideand 42.5 parts of sodium carbonate in 300 parts of water and stirring iscontinued for 3 hours at pH 8-9. The dyestuff of the structure ##STR26##which has separated out at pH 7.5 is filtered off and dried.

The trisazo dyestuff dyes cotton in orange-red colour shades. Thedyeings are distinguished by a good depth of colour and good fastnessproperties, in particular by good fastness to washing, water andperspiration.

Trisazo dyestuffs which dye cotton and viscose in orange-red colourshades are obtained if 3-methylaniline, 3-methoxyaniline,2,5-dimethylaniline, 2-methoxy-5-chloroaniline, 2,5-dimethoxyaniline,1-amino-3-formanilide, 1-amino-3-acetylaminobenzene,1-amino-3-acetylamino-6-methylbenzene, 1-amino-3-oxalylaminobenzene,1-amino-3-oxalylamino-6-methylbenzene, 3-aminophenol,1-amino-3-acetylamino-6-methoxybenzene,1-amino-3-acetylamino-6-ethoxybenzene or 2-ethoxy-5-methylaniline, areused as the diazotisable coupling component instead of2-methoxy-5-methylaniline or if the coupling components1-(2'-sulphophenyl)-3-methyl-5-pyrazolone,1-(3'-sulphophenyl)-3-methyl-5-pyrazolone,1-(2'-nitro-4'-sulphophenyl)-3-methyl-5-pyrazolone,1-(4'-nitro-2'-sulphophenyl)-3-methyl-5-pyrazolone,1-(2',5'-dichloro-4'-sulphophenyl)-3-methyl-5-pyrazolone,1-(2'-methyl-6'-chloro-4'-sulphophenyl)-3-methyl-5-pyrazolone,1-(2',4'-disulphophenyl)-3-methyl-5-pyrazolone,1-(2',5'-disulphophenyl)-3-methyl-5 -pyrazolone,1-(4'-sulphophenyl)-5-pyrazolone-3-carboxylic acid methyl ester,1-(4'-sulphophenyl)-5-pyrazolone-3-carboxylic acid ethyl ester,1-(2'-sulphophenyl)-5-pyrazolone-3-carboxylic acid,1-(3'-sulphophenyl)-5-pyrazolone-3-carboxylic acid,1-(4'-sulphophenyl)-5-pyrazolone-3-carboxylic acid,1-(2'-carboxyphenyl)-5-pyrazolone-3-carboxylic acid or1-(2',5'-dichloro-4'-sulphophenyl)-5-pyrazolone-3-carboxylic acid areused instead of 1-(4'-sulphophenyl)-3-methyl-5-pyrazolone. The dyeingsare also distinguished by a good depth of colour and good fastnessproperties, in particular by good fastness to water, washing andperspiration.

EXAMPLE 4

The tetrazotised monoazo dyestuff of the formula ##STR27## is preparedaccording to the instructions of Example 2.

The solution of this tetrazo compound is then run, at 0°-5° C., into asolution of 44.6 parts of 1-aminonaphthalene-6-sulphonic acid, 8 partsof sodium hydroxide and 42.5 parts of sodium carbonate in 350 parts ofwater. Stirring is continued for 3-4 hours a pH 7.5-8.5. The trisazodyestuff of the structure ##STR28## which has separated out at pH 5 isfiltered off and dried. Brown dyeings of a good depth of colour and withgood fastness properties, for example good fastness to water, washingand perspiration, are obtained on cotton or regenerated cellulose.

Brown trisazo dyestuffs which are also distinguished by a hightinctorial strength and good fastness to water, washing andperspiration, are obtained if the diazotisable coupling components3-methylaniline, 3-methoxyaniline, 3-aminophenol, 2,5-dimethylaniline,2-methoxy-5-chloroaniline, 2,5-dimethoxyaniline, 1-amino-3-formanilide,1-amino-3-acetylaminobenzene, 1-amino-3-acetylamino-6-methylbenzene,1-amino-3-oxalylaminobenzene, 1-amino-3-oxalylamino-6-methylbenzene,1-amino-3-acetylamino-6-methoxybenzene,1-amino-3-acetylamino-6-ethoxybenzene or 2-ethoxy-5-methylaniline areemployed instead of 2-methoxy-5-methylaniline or if the couplingcomponents 1-aminonaphthalene-7-sulphonic acid, the technical mixture of1-aminonaphthalene-6-sulphonic acid and 1-aminonaphthalene-7-sulphonicacid, 1-aminonaphthalene-4-sulphonic acid,2-aminonaphthalene-6-sulphonic acid,1-phenylaminonaphthalene-8-sulphonic acid,2-aminonaphthalene-3,6-disulphonic acid,2-aminonaphthalene-6,8-disulphonic acid,1-carboxymethylaminonaphthalene-6-sulphonic acid,1-carboxymethylamino-naphthalene-7-sulphonic acid or the couplingcomponents of the benzene series 1,3-dihydroxybenzene-4-sulphonic acid,1,3-dihydroxybenzene-5-sulphonic acid, 3-aminophenol-4-sulphonic acid,3-aminophenol-6-sulphonic acid, 1,3-diaminobenzene-4-sulphonic acid,1-acetylamino-3-aminobenzene-4-sulphonic acid,2,4-diaminotoluene-5-sulphonic acid, 2,6-diaminotoluene-4-sulphonicacid, 1,3-diaminobenzene-4,6-disulphonic acid,3-carboxymethylaminophenol, 1-amino-3-carboxymethylaminobenzene,1amino-3-carboxymethylaminobenzene,1-amino-3-carboxymethylamino-6-methylbenzene,1,3-biscarboxymethylaminobenzene,1,3-biscarboxymethylamino-6-methylbenzene, 2-hydroxybenzoic acid,2-hydroxybenzene-sulphonic acid, 3-hydroxybenzene-sulphonic acid,4-hydroxybenzene-sulphonic acid, 2-hydroxy-5-sulphobenzoic acid or2-hydroxy-3-methylbenzoic acid are employed instead of1-aminonaphthalene-6-sulphonic acid.

EXAMPLE 5

A solution of the tetrazotised monoazo dyestuff of the formula ##STR29##is prepared according to the instructions of Example 2 and is adjustedto pH 3 at 0°-5° C. with a solution of 7 parts of sodium acetate in 50parts of water. A solution of 31.9 parts of1-amino-8-hydroxynaphthalene-3,6-disulphonic acid, 4 parts of sodiumhydroxide and 36 parts of sodium carbonate in 200 parts of water is thenrun in in the course of approximately 10 minutes. Stirring is continuedfor approximately 15 minutes at pH 7.5-8 until the one-sided coupling iscomplete and a solution of 23.9 parts of2-amino-8-hydroxynaphthalene-6-sulphonic acid, 4 parts of sodiumhydroxide and 14 parts of sodium carbonate in 150 parts of water is thenadded rapidly to the coupling mixture. Stirring is continued for 3 hoursat 0°-5° C. and at pH 8.5-9 in order to complete the coupling reaction.

The trisazo dyestuff of the structure ##STR30## which has separated outat pH 7.5 with the aid of 150 parts of sodium chloride is filtered offand dried.

On cotton or regenerated cellulose the resulting dyestuff gives darkblue colour shades of a good depth of colour and with good fastnessproperties, in particular with good fastness to water and washing andvery good fastness to perspiration.

Trisazo dyestuffs with a blue to blue-black shade and with similarlygood fastness properties, in particular good fastness to washing, towater and perspiration, are obtained if the diazotisable couplingcomponents 3-methylaniline, 3-methoxyaniline, 3-aminophenol,2,5-dimethylaniline, 2-methoxy-5-chloroaniline, 2,5-dimethoxyaniline,1-amino-3-formanilide, 1-amino-3-acetylaminobenzene,1-amino-3-acetylamino-6-methylbenzene, 1-amino-3-oxalylaminobenzene,1-amino-3-oxalylamino-6-methylbenzene,1-amino-3-acetylamino-6-methoxybenzene,1-amino-3-acetylamino-6-ethoxybenzene or 2-ethoxy-5-methylaniline areemployed instead of 2-methoxy-5-methylaniline or if the couplingcomponents 1-acetylamino-8-hydroxynaphthalene-3,6-disulphonic acid,1-benzoylamino-8-hydroxynaphthalene-3,6-disulphonic acid,1-amino-8-hydroxy-2,4-disulphonic acid,1-amino-8-hydroxy-4,6-disulphonic acid or1-amino-8-hydroxynaphthalene-4-sulphonic acid are employed instead of1-amino-8-hydroxynaphthalene-3,6-disulphonic acid or if the couplingcomponents 2-carboxymethylamino-8-hydroxynaphthalene-6-sulphonic acid,2-methylamino-8-hydroxynaphthalene-6-sulphonic acid,2-dimethylamino-8-hydroxynaphthalene-6-sulphonic acid,2-phenylamino-8-hydroxynaphthalene-6-sulphonic acid,2-hydroxyethylamino-8-hydroxynaphthalene-6-sulphonic acid,2-acetylamino-8-hydroxynaphthalene-6-sulphonic acid,2-amino-5-hydroxynaphthalene-7-sulphonic acid,2-phenylamino-5-hydroxynaphthalene-7-sulphonic acid,2-carboxymethylamino-5-hydroxynaphthalene-7-sulphonic acid,2-acetylamino-5-hydroxynaphthalene-7-sulphonic acid or2-amino-8-hydroxynaphthalene-3,6-disulphonic acid are employed insteadof 2-amino-8-hydroxynaphthalene-6-sulphonic acid.

The structure of further dyestuffs which can be prepared in accordancewith Examples 1 to 5 can be seen from the Table.

The following information is given in the Table:

In column 1

The coupling component B₁ -H (XII) used

In column 2

The diazotisable coupling component M-NH₂ of the formula Vc ##STR31##which has been used.

In column 3

Heterocyclic diamine used, heterocyclic diamines of the formula##STR32## that is to say the 5-isomers, being listed in Table I andheterocyclic diamines of the formula ##STR33## that is to say the6-isomers, being listed in Table II. The first position in column 3indicates the meaning of --X--. In addition, column 3 also listssubstituents which may be present and their positions in the molecule,the numbering being indicated above. The entry "--NH--, 4-CH₃ " incolumn 3 of Table I, for example, thus denotes the compound ##STR34##Owing to the possibility of tautomerism, this compound can be designated4-methyl-2-(4'-aminophenyl)-5-aminobenzimidazole or7-methyl-2-(4'-aminophenyl)-6-aminobenzimidazole.

In column 4

The coupling component B₂ H (X) used.

In column 5

The colour shade of the dyestuff on cotton.

                                      Table I                                     __________________________________________________________________________     Coupling component                                                                           Diazotisable Coupling component                                                          ##STR35##       Coupling component                                                                            Colour shade                                                                 on                  B.sub.1H       MNH.sub.2  X -             B.sub.2H        cotton              __________________________________________________________________________    1-Hydroxynaphthalene-                                                                        2-Methoxy-5-methyl-                                                                      NH              1-Hydroxynaphthalene-                                                                        blue-                4-sulphonic acid                                                                             aniline                    4-sulphonic acid                                                                             violet               1-Hydroxynaphthalene-                                                                        "          "               1-Hydroxynaphthalene-                                                                        "                    5-sulphonic acid                          5-sulphonic acid                    2-Hydroxynaphthalene-                                                                        "          "               2-Hydroxynaphthalene-                                                                        "                    3,6-disulphonic acid                      3,6-disulphonic acid                2-Hydroxynaphthalene-                                                                        "          "               2-Hydroxynaphthalene-                                                                        "                    6,8-disulphonic acid                      6,8-disulphonic acid                2-Hydroxynaphthalene-                                                                        "          "               2-Hydroxynaphthalene-                                                                        "                    8-sulphonic acid                          8-sulphonic acid                    2-Amino-5-hydroxy-                                                                           "          "               2-Amino-5-hydroxy-                                                                           brown-               naphthalene-7-                            naphthalene-7- violet               sulphonic acid                            sulphonic acid                      2-Carboxymethylamino-                                                                        "          "               2-Carboxymethylamino-                                                                        "                    5-hydroxynaphthalene-                     5-hydroxynaphthalene-               7-sulphonic acid                          7-sulphonic acid                    2-Carboxymethylamino-                                                                        "          "               2-Carboxymethylamino-                                                                        blue-                8-hydroxynaphthalene-                     8-hydroxynaphthalene-                                                                        black                6-sulphonic acid                          6-sulphonic acid                    2-Hydroxyethylamino-                                                                         2-Methoxy-5-methyl-                                                                      NH              2-Hydroxyethylamino-                                                                         blue-                8-hydroxynaphthalene-                                                                        aniline                    8-hydroxynaphthalene-                                                                        black                6-sulphonic acid                          6-sulphonic acid                    2-Sulphomethylamino-                                                                         "          "               2-Sulphomethylamino-                                                                         "                    8-hydroxynaphthalene-                     8-hydroxynaphthalene-               6-sulphonic acid                          6-sulphonic acid                    Acetoacetic acid                                                                             2-Methoxy-5-methyl-                                                                      NH              Acetoacetic acid                                                                             orange               2-sulphoanilide                                                                              aniline                    2-sulphoanilide                     Acetoacetic acid                                                                             "          NH              Acetoacetic acid                                                                             "                    3-sulphoanilide                           3-sulphoanilide                     Acetoacetic acid                                                                             "          NH              Acetoacetic acid                                                                             "                    4-sulphoanilide                           4-sulphoanilide                     Acetoacetic acid                                                                             "          NH              Acetoacetic acid                                                                             "                    2-methoxy-4-                              2-methoxy-4-                        sulphoanilide                             sulphoanilide                       Acetoacetic acid                                                                             "          NH              Acetoacetic acid                                                                             "                    2-methoxy-5-                              2-methoxy-5-                        sulphoanilide                             sulphoanilide                       Acetoacetic acid                                                                             "          NH              Acetoacetic acid                                                                             "                    2-sulpho-4-chloro-                        2-sulpho-4-chloro-                  5-methylanilide                           5-methylanilide                     Acetoacetic acid 2-                                                                          2-Methoxy-5-methyl-                                                                      NH              Acetoacetic acid                                                                             orange               sulpho-4,6-    aniline                    sulpho-4,6-                         dimethylanilide                           dimethylanilide                     Acetoacetic acid                                                                             "          NH              Acetoacetic acid                                                                             "                    2,4-disulphoanilide                       2,4-disulphoanilide                 Acetoacetic acid                                                                             "          NH              Acetoacetic acid                                                                             "                    2,5-disulphoanilide                       2,5-disulphoanilide                 2-Hydroxybenzoic                                                                             "          NH              2-Hydroxy-3-methyl-                                                                          orange-              acid                                      benzoic acid   brown                  "            "          NH              1-Carboxymethylamino-                                                                        "                                                              3-aminobenzene                        "            "          NH              2-Hydroxybenzene-                                                                            "                                                              sulphonic acid                        "            "          NH              1,3-Dihydroxy- "                                                              benzene-4-                                                                    sulphonic acid                        "            "          NH              1,3-Dihydroxy- "                                                              benzene-5-                                                                    sulphonic acid                        "            "          NH              1-Carboxymethylamino-                                                                        "                                                              3-amino-4-methyl-                                                             benzene                             2-Hydroxybenzoic                                                                             2-Methoxy-5-methyl-                                                                      NH              3-Aminophenol-4-                                                                             orange-              acid           aniline                    sulphonic acid brown                  "            "          NH              1,3-Diaminobenzene-                                                                          "                                                              4-sulphonic acid                      "            "          NH              2,4-Diaminotoluene-                                                                          "                                                              5-sulphonic acid                      "            "          NH              1,3-Diaminobenzene-                                                                          "                                                              4,6-disulphonic acid                  "            "          NH              3-Carboxymethylamino-                                                                        "                                                              phenol                                "            "          NH              1,3-Biscarboxymethyl-                                                                        "                                                              aminobenzene                          "            "          NH              2,4-Biscarboxymethyl-                                                                        "                                                              aminotoluene                          "            "          NH              1-Aminonaphthalene-4-                                                                        "                                                              sulphonic acid                        "            "          NH              1-Aminonaphthalene-6-                                                                        "                                                              sulphonic acid                        "            "          NH              1-Aminonaphthalene-7-                                                                        "                                                              sulphonic acid                      2-Hydroxybenzoic                                                                             2-Methoxy-5-methyl-                                                                      NH              1-Carboxymethylamino-                                                                        orange-              acid           aniline                    naphthalene-6- brown                                                          sulphonic acid                        "            "          NH              1-Carboxymethylamino-                                                                        "                                                              naphthalene-7-                                                                sulphonic acid                        "            "          NH              1-Phenylamino- "                                                              naphthalene-8-                                                                sulphonic acid                        "            "          NH              1-Aminonaphthalene-                                                                          "                                                              3,6-disulphonic acid                  "            "          NH              2-Aminonaphthalene-                                                                          "                                                              3,6-disulphonic acid                  "            "          NH              2-Aminonaphthalene-                                                                          "                                                              4,8-disulphonic acid                  "            "          NH              1-Hydroxynaphthalene-                                                                        orange-red                                                     4-sulphonic acid                      "            "          NH              1-Hydroxynaphthalene-                                                                        "                                                              5-sulphonic acid                      "            "          NH              2-Hydroxynaphthalene-                                                                        "                                                              6-sulphonic acid                    2-Hydroxybenzoic                                                                             2-Methoxy-5-methyl-                                                                      NH              2-Hydroxynaphthalene-                                                                        orange-red           acid           aniline                    8-sulphonic acid                      "            "          NH              2-Hydroxynaphthalene-                                                                        "                                                              3,6-disulphonic acid                  "            "          NH              2-Hydroxynaphthalene-                                                                        "                                                              6,8-disulphonic acid                  "            "          NH              1-Amin-8-hydroxy-                                                                            green                                                          naphthalene-3,6-                                                              disulphonic acid                      "            "          NH              1-Acetylamino-8-                                                                             "                                                              hydroxynaphthalene-                                                           3,6-disulphonic acid                2-Hydroxy-3-methyl-                                                                          "          NH              1-Amino-8-hydroxy-                                                                           "                    benzoic acid                              naphthalene-3,6-                                                              disulphonic acid                    2-Hydroxybenzene-                                                                            "          NH                "            "                    sulphonic acid                                                                2-Hydroxybenzoic                                                                             "          NH              Acetoacetic acid                                                                             yellow-              acid                                      2-sulphoanilide                                                                              orange                 "            "          NH              Acetoacetic acid                                                                             "                                                              3-sulphoanilide                     2-Hydroxybenzoic                                                                             2-Methoxy-5-methyl-                                                                      NH              Acetoacetic acid                                                                             yellow-              acid           aniline                    sulphoanilide  orange                 "            "          NH              Acetoacetic acid                                                                             "                                                              2,4-disulphoanilide                   "            "          NH              Acetoacetic acid                                                                             "                                                              2,5-disulphoanilide                 2-Hydroxy-3-methyl-                                                                          "          NH              Acetoacetic acid                                                                             "                    benzoic acid                              3-sulphoanilide                     2-Hydroxybenzoic                                                                             "          NH              1-(2'-Sulphophenyl)-                                                                         orange               acid                                      3-methyl-5-                                                                   pyrazolone                            "            "          NH              1-(3'-Sulphophenyl)-                                                                         "                                                              3-methyl-5-                                                                   pyrazolone                            "            "          NH              1-(4'-Sulphophenyl)-                                                                         "                                                              3-methyl-5-                                                                   pyrazolone                            "            "          NH              1-(2'-Nitro-4'-                                                                              "                                                              sulphophenyl)-3-                                                              methyl-5-pyrazolone                 2-Hydroxybenzoic                                                                             2-Methoxy-5-methyl-                                                                      NH              1-(4'-Nitro-2'-                                                                              orange               acid           aniline                    sulphophenyl)-3-                                                              methyl-5-pyrazolone                   "            "          NH              1-(2',5'-Dichloro-                                                                           "                                                              4'-sulphophenyl)-3-                                                           methyl-5-pyrazolone                   "            "          NH              1-(2'-Methyl-6'-                                                                             "                                                              chloro-4'-sulpho-                                                             phenyl)-3-methyl-5-                                                           pyrazolone                            "            "          NH              1-(2',4'-Disulpho-                                                                           "                                                              phenyl)-3-methyl-5-                                                           pyrazolone                            "            "          NH              1-(2',5'-Disulpho-                                                                           "                                                              phenyl)-3-methyl-5-                                                           pyrazolone                            "            "          NH              1-(4'-Sulphophenyl)-                                                                         orange-red                                                     5-pyrazolone-3-                                                               carboxylic acid                                                               methyl ester                          "            "          NH              1-(2'-Sulphophenyl)-                                                                         "                                                              5-pyrazolone-3-                                                               carboxylic acid                     2-Hydroxybenzoic acid                                                                        2-Methoxy-5-methyl-                                                                      NH              1-(3'-Sulphophenyl)-                                                                         orange-red                          aniline                    5-pyrazolone-3-                                                               carboxylic acid                       "            "          NH              1-(4'-Sulphophenyl)-                                                                         "                                                              5-pyrazolone-3-                                                               carboxylic acid                       "            "          NH              1-(2'-Carboxyphenyl)-                                                                        "                                                              5-pyrazolone-3-                                                               carboxylic acid                       "            "          NH              1-(2',5'-Dichloro-                                                                           "                                                              4'-sulphophenyl)-5-                                                           pyrazolone-3-                                                                 carboxylic acid                     2-Hydroxy-3-methyl-                                                                          "          NH              1-(4'-Sulphophenyl)-                                                                         "                    benzoic acid                              3-methyl-5-                                                                   pyrazolone                            "            "          NH              1-(2',4'-Disulpho-                                                                           "                                                              phenyl)-3-methyl-5-                                                           pyrazolone                            "            "          NH              1-(2',5'-Disulpho-                                                            phenyl)-3-methyl-5-                                                           pyrazolone                          2-Hydroxy-3-methyl-                                                                          2-Methoxy-5-methyl-                                                                      NH              1-(4'-Sulphophenyl)-                                                                         orange-red           benzoic acid   aniline                    5-pyrazolone-3-                                                               carboxylic acid                     1-Aminonaphthalene-                                                                          "          NH              3-Aminophenol-4-                                                                             brown                4-sulphonic acid                          sulphonic acid                        "            "          NH              1,3-Diaminobenzene-                                                                          "                                                              4-sulphonic acid                    1-Hydroxynaphthalene-                                                                        "          NH              1,3-Diaminobenzene-                                                                          brown-red            4-sulphonic acid                          4-sulphonic acid                      "            "          NH              1-Carboxymethyl-                                                                             "                                                              amino-3-aminobenzene                2-Hydroxynaphthalene-                                                                        "          NH              1,3-Diaminobenzene                                                                           "                    3,6-disulphonic acid                                                            "            "          NH              Phenol         "                      "            "          NH              2-Hydroxybenzoic                                                                             "                                                              acid                                  "            "          NH              3-Aminophenol  "                      "            "          NH              1,3-Dihydroxybenzene                                                                         "                    2-Hydroxynaphthalene-                                                                        2-Methoxy-5-methyl-                                                                      NH              1,3-Diamino-4- brown-red            3,6-disulphonic acid                                                                         aniline                    methylbenzene                         "            "          NH              1,3-Diamino-4- "                                                              methoxybenzene                        "            "          NH              1,3-Diamino-4- "                                                              chlorobenzene                         "            "          NH              1,3-Diamino-4- "                                                              nitrobenzene                        2-Hydroxynaphthalene-                                                                        "          NH              1,3-Diaminobenzene                                                                           "                    6,8-disulphonic acid                                                          1-Aminonaphthalene-                                                                          "          NH              1-Hydroxynaphthalene-                                                                        "                    4-sulphonic acid                          4-sulphonic acid                      "            "          NH              1-Hydroxynaphthalene-                                                                        "                                                              5-sulphonic acid                      "            "          NH              2-Hydroxynaphthalene-                                                                        "                                                              6-sulphonic acid                      "            "          NH              2-Hydroxynaphthalene-                                                                        "                                                              8-sulphonic acid                      "            "          NH              2-Hydroxynaphthalene-                                                                        "                                                              3,6-disulphonic acid                1-Aminonaphthalene-                                                                          2-Methoxy-5-methyl-                                                                      NH              2-Hydroxynaphthalene-                                                                        brown-red            4-sulphonic acid                                                                             aniline                    6,8-disulphonic acid                2-Hydroxynaphthalene-                                                                        "          NH              1-Phenylamino- "                    3,6-disulphonic acid                      naphthalene-8-                                                                sulphonic acid                        "            "          NH              1-Amino-8-hydroxy-                                                                           blue                                                           naphthalene-4-                                                                sulphonic acid                        "            "          NH              1-Amino-8-hydroxy-                                                                           "                                                              naphthalene-3,6-                                                              disulphonic acid                      "            "          NH              1-Acetylamino-8-                                                                             "                                                              hydroxynaphthalene-                                                           3,6-disulphonic acid                  "            "          NH              2-Amino-8-hydroxy-                                                                           "                                                              naphthalene-6-                                                                sulphonic acid                        "            "          NH              2-Amino-5-hydroxy-                                                                           blue-                                                          naphthalene-7- violet                                                         sulphonic acid                      1-Hydroxynaphthalene-                                                                        "          NH              1-Hydroxynaphthalene-                                                                        "                    4-sulphonic acid                          5-sulphonic acid                    1-Hydroxynaphthalene-                                                                        2-Methoxy-5-methyl-                                                                      NH              2-Hydroxynaphthalene-                                                                        blue-                4-sulphonic acid                                                                             aniline                    6-sulphonic acid                                                                             violet                 "            "          NH              2-Hydroxynaphthalene-                                                                        "                                                              8-sulphonic acid                      "            "          NH              2-Hydroxynaphthalene-                                                                        "                                                              3,6-disulphonic acid                  "            "          NH              2-Hydroxynaphthalene-                                                                        "                                                              6,8-disulphonic acid                  "            "          NH              1-Aminonaphthalene-                                                                          brown-red                                                      4-sulphonic acid                      "            "          NH              1-Aminonaphthalene-                                                                          "                                                              6-sulphonic acid                    2-Hydroxynaphthalene-                                                                        "          NH              1-Hydroxynaphthalene-                                                                        blue-                3,6-disulphonic acid                      4-sulphonic acid                                                                             violet                 "            "          NH              1-Hydroxynaphthalene                                                                         "                      "            "          NH              2-Hydroxynaphthalene                                                                         "                      "            "          NH              2-Hydroxy-2-   "                                                              naphthoic acid                      2-Hydroxynaphthalene-                                                                        2-Methoxy-5-methyl-                                                                      NH              1-Hydroxynaphthalene-                                                                        blue-                3,6-disulphonic acid                                                                         aniline                    5-sulphonic acid                                                                             violet                 "            "          NH              2-Hydroxynaphthalene-                                                                        "                                                              6-sulphonic acid                      "            "          NH              2-Hydroxynaphthalene-                                                                        "                                                              8-sulphonic acid                      "            "          NH              2-Hydroxynaphthalene-                                                                        "                                                              6,8-disulphonic acid                2-Hydroxynaphthalene-                                                                        "          NH              1-Hydroxynaphthalene                                                                         "                    6,8-disulphonic acid                                                            "            "          NH              2-Hydroxynaphthalene                                                                         "                      "            "          NH              1-Hydroxynaphthalene-                                                                        "                                                              4-sulphonic acid                    1-Aminonaphthalene-                                                                          "          NH              Acetoacetic acid                                                                             orange-              4-sulphonic acid                          3-sulphoanilide                                                                              brown                1-Aminonaphthalene-                                                                          "          NH              Acetoacetic acid                                                                             "                    6-sulphonic acid                          3-sulphoanilide                     1-Hydroxynaphthalene-                                                                        "          NH              Acetoacetic acid                                                                             orange-red           4-sulphonic acid                          3-sulphoanilide                     1-Hydroxynaphthalene-                                                                        2-Methoxy-5-methyl-                                                                      NH              Acetoacetic acid                                                                             orange-red           5-sulphonic acid                                                                             aniline                    3-sulphoanilide                     2-Hydroxynaphthalene-                                                                        "          NH              Acetoacetic acid                                                                             "                    3,6-disulphonic acid                      anilide                               "            "          NH              Acetoacetic acid                                                                             "                                                              2-methoxyanilide                      "            "          NH              Acetoacetic acid                                                                             "                                                              4-methoxyanilide                      "            "          NH              Acetoacetic acid                                                                             "                                                              4-ethoxyanilide                       "            "          NH              Acetoacetic acid                                                                             "                                                              o-toluidide                           "            "          NH              Acetoacetic acid                                                                             "                                                              m-toluidide                           "            "          NH              Acetoacetic acid                                                                             "                                                              p-toluidide                           "            "          NH              Acetoacetic acid                                                                             "                                                              2-chloroanilide                       "            "          NH              Acetoacetic acid                                                                             "                                                              4-chloroanilide                     2-Hydroxynaphthalene-                                                                        2-Methoxy-5-methyl-                                                                      NH              1-Phenyl-3-methyl-5-                                                                         red-                 3,6-disulphonic acid                                                                         aniline                    pyrazolone     violet                 "            "          NH              1-(4'-Methylphenyl)-                                                                         "                                                              3-methyl-5-pyrazolone               2-Hydroxynaphthalene-                                                                        "          NH              1-Phenyl-3-methyl-5-                                                                         "                    6,8-disulphonic acid                      pyrazolone                          1-Hydroxynaphthalene                                                                         "          NH              1-(4'-Sulphophenyl)-                                                                         "                                                              5-pyrazolone-3-                                                               carboxylic acid                     2-Hydroxynaphthalene                                                                         "          NH                "            "                    2-Hydroxynaphthalene-                                                                        "          NH                "            "                    3-carboxylic acid                                                             2-Hydroxynaphthalene                                                                         "          NH              1-(2',5'-Disulpho-                                                                           "                                                              phenyl)-3-methyl-5-                                                           pyrazolone                          2-Hydroxynaphthalene-                                                                        "          NH              1-(4'-Sulphophenyl)-                                                                         "                    3-carboxylic acid                         3-methyl-5-pyrazolone               1-Hydroxynaphthalene-                                                                        "          NH              4-Methyl-6-hydroxy-                                                                          "                    4-sulphonic acid                          2-pyridone-3-                                                                 sulphonic acid                      2-Hydroxynaphthalene-                                                                        2-Methoxy-5-methyl-                                                                      NH              4-Methyl-6-hydroxy-                                                                          red-                 3,6-disulphonic acid                                                                         aniline                    2-pyridone-3-  violet                                                         sulphonic acid                        "            "          NH              1,4-Dimethyl-6-                                                                              "                                                              hydroxy-2-pyridone-                                                           3-sulphonic acid                      "            "          NH              4-Methyl-3-cyano-6-                                                                          "                                                              hydroxy-2-pyridone                    "            "          NH              1,4-Dimethyl-3-                                                                              "                                                              cyano-6-hydroxy-2-                                                            pyridone                            Acetoacetic acid                                                                             "          NH              1-Hydroxynaphthalene-                                                                        red-                 3-sulphoanilide                           4-sulphonic acid                                                                             orange                 "            "          NH              2-Hydroxynaphthalene-                                                                        "                                                              3,6-disulphonic acid                  "            "          NH              1,3-Diaminobenzene-                                                                          brown-                                                         4-sulphonic acid                                                                             orange                 "            "          NH              2,4-Diaminotoluene-                                                                          "                                                              5-sulphonic acid                      "            "          NH              3-Carboxymethylamino-                                                                        "                                                              phenol                              Acetoacetic acid                                                                             2-Methoxy-5-methyl-                                                                      NH              1-Carboxymethyl-                                                                             brown-               3-sulphoanilide                                                                              aniline                    amino-3-amino- orange                                                         benzene                               "            "          NH              1,3-Biscarboxy-                                                                              "                                                              methylaminobenzene                    "            "          NH              1-Carboxymethyl-                                                                             "                                                              amino-3-amino-4-                                                              methylbenzene                       Acetoacetic acid                                                                             "          NH              1,3-Diaminobenzene-                                                                          "                    anilide                                   4,6-disulphonic acid                Acetoacetic acid                                                                             "          NH              1,3-Dihydroxybenzene                                                                         "                    2,5-disulphoanilide                                                             "            "          NH              3-Aminophenol  "                      "            "          NH              1,3-Diaminobenzene                                                                           "                      "            "          NH              2,4-Diaminotoluene                                                                           "                    Acetoacetic acid                                                                             "          NH              1-Aminonaphthalene-                                                                          orange-              3-sulphoanilide                           4-sulphonic acid                                                                             brown                  "            "          NH              1-Aminonaphthalene-                                                                          "                                                              5-sulphonic acid                      "            "          NH              1-Aminonaphthalene-                                                                          "                                                              6-sulphonic acid                    Acetoacetic acid                                                                             2-Methoxy-5-methyl-                                                                      NH              1-Aminonaphthalene-                                                                          orange-              3-sulphoanilide                                                                              aniline                    7-sulphonic acid                                                                             brown                  "            "          NH              1-Carboxymethyl-                                                                             "                                                              aminonaphthalene-6-                                                           sulphonic acid                        "            "          NH              1-Carboxymethyl-                                                                             "                                                              aminonaphthalene-7-                                                           sulphonic acid                        "            "          NH              2-Aminonaphthalene-                                                                          "                                                              6-sulphonic acid                      "            "          NH              1-Phenylamino- "                                                              naphthalene-8-                                                                sulphonic acid                        "            "          NH              2-Amino-8-hydroxy-                                                                           brown                                                          naphthalene-6-                                                                sulphonic acid                      Acetoacetic acid                                                                             "          NH                "            "                    2-sulphoanilide                                                               Acetoacetic acid                                                                             "          NH                "            "                    4-sulphoanilide                                                               Acetoacetic acid                                                                             "          NH                "            "                    4-carboxyanilide                                                              Acetoacetic acid                                                                             2-Methoxy-5-                                                                             NH              2-Amino-8-hydroxy-                                                                           brown                2,5-disulphoanilide                                                                          methylaniline              naphthalene-6-                                                                sulphonic acid                      Acetoacetic acid                                                                             "          NH              2-Methylamino-8-                                                                             "                    3-sulphoanilide                           hydroxynaphthalene-                                                           6-sulphonic acid                      "            "          NH              2-Dimethylamino-8-                                                                           "                                                              hydroxynaphthalene-                                                           6-sulphonic acid                      "            "          NH              2-Phenylamino-8-                                                                             "                                                              hydroxynaphthalene-                                                           6-sulphonic acid                      "            "          NH              2-Acetylamino-8-                                                                             brown-red                                                      hydroxynaphthalene-                                                           6-sulphonic acid                      "            "          NH              2-Acetylamino-5-                                                                             "                                                              hydroxynaphthalene-                                                           7-sulphonic acid                      "            "          NH              1-Amino-8-hydroxy-                                                                           green                                                          naphthalene-3,6-                                                              disulphonic acid                    Acetoacetic acid                                                                             "          NH              1-Amino-8-hydroxy-                                                                           "                    4-carboxyanilide                          naphthalene-3,6-                                                              disulphonic acid                    Acetoacetic acid                                                                             2-Methoxy-5-methyl-                                                                      NH              2-Carboxymethyl-                                                                             brown                3-sulphoanilide                                                                              aniline                    amino-8-hydroxy-                                                              naphthalene-6-                                                                sulphonic acid                        "            "          NH              2-Amino-5-hydroxy-                                                                           red-brown                                                      naphthalene-7-                                                                sulphonic acid                        "            "          NH              Acetoacetic acid                                                                             orange                                                         2-sulphoanilide                       "            "          NH              Acetoacetic acid                                                                             "                                                              4-sulphoanilide                     Acetoacetic acid                                                                             "          NH              Acetoacetic acid                                                                             "                    4-carboxyanilide                          3-sulphoanilide                       "            "          NH              Acetoacetic acid                                                                             "                                                              2,5-disulphoanilide                 Acetoacetic acid                                                                             "          NH              Acetoacetic acid                                                                             "                    2,5-disulphoanilide                       anilide                               "            "          NH              Acetoacetic acid                                                                             "                                                              2-methoxyanilide                      "            "          NH              Acetoacetic acid                                                                             "                                                              4-methoxyanilide                    Acetoacetic acid                                                                             2-Methoxy-5-methyl-                                                                      NH              1-(2'-Sulphophenyl)-                                                                         orange               3-sulphoanilide                                                                              aniline                    3-methyl-5-pyrazolone                 "            "          NH              1-(3'-Sulphophenyl)-                                                                         "                                                              3-methyl-5-pyrazolone                 "            "          NH              1-(4'-Sulphophenyl)-                                                                         "                                                              3-methyl-5-pyrazolone                 "            "          NH              1-(2'-chloro-4'-                                                                             "                                                              sulphophenyl)-3-                                                              methyl-5-pyrazolone                   "            "          NH              1-(6'-chloro-3'-                                                                             "                                                              sulphophenyl)-3-                                                              methyl-5-pyrazolone                   "            "          NH              1-(2',5'-dichloro-                                                                           "                                                              4'-sulphophenyl)-3-                                                           methyl-5-pyrazolone                   "            "          NH              1-(2',4'-Disulpho-                                                                           "                                                              phenyl)-3-methyl-5-                                                           pyrazolone                            "            "          NH              1-(2',5'-Disulpho-                                                                           "                                                              phenyl)-3-methyl-5-                                                           pyrazolone                          Acetoacetic acid                                                                             2-Methoxy-5-methyl-                                                                      NH              1-Phenyl-5-pyrazo-                                                                           orange               3-sulphoanilide                                                                              aniline                    lone-3-carboxylic                                                             acid                                  "            "          NH              1-(4'-Sulphophenyl)-                                                                         "                                                              5-pyrazolone-3-                                                               carboxylic acid                       "            "          NH              1-(4'-Sulphophenyl)-                                                                         "                                                              5-pyrazolone-3-                                                               carboxylic acid ester                 "            "          NH              1-(2',5'-dichloro-4'-                                                                        "                                                              sulphophenyl)-5-                                                              pyrazolone-3-                                                                 carboxylic acid                       "            "          NH              4-Methyl-6-hydroxy-2-                                                                        orange-red                                                     pyridone-3-sulphonic                                                          acid                                  "            "          NH              1,4-Dimethyl-6-                                                                              "                                                              hydroxy-2-pyridone-                                                           3-sulphonic acid                    1-(2',4'-Disulpho-                                                                           "          NH              1,3-Diaminobenzene                                                                           brown                phenyl)-3-methyl-                                                             5-pyrazolone                                                                  1-(2',5'-Disulpho-                                                                           2-Methoxy-5-methyl-                                                                      NH              Phenol         orange               phenyl)-3-methyl-                                                                            aniline                                                        5-pyrazolone                                                                    "            "          NH              1,3-dihydroxybenzene                                                                         orange-                                                                       brown                  "            "          NH              3-Aminophenol  brown                  "            "          NH              1,3-Diaminobenzene                                                                           "                      "            "          NH              2,4-Diaminotoluene                                                                           "                    1-(4'-Sulphophenyl)-                                                                         "          NH              1-Amino-8-hydroxy-                                                                           black-               5-pyrazolone-3-                           naphthalene-3,6-                                                                             green                carboxylic acid                           disulphonic acid                    1-Phenyl-5-    "          NH                "            "                    pyrazolone-3-                                                                 carboxylic acid                                                               1-(4'-Sulphophenyl)-                                                                         "          NH                "            "                    3-methyl-5-pyrazolone                                                           "            "          NH              1-Aminonaphthalene-                                                                          red-                                                           4-sulphonic acid                                                                             brown                  "            "          NH              1-Aminonaphthalene-                                                                          "                                                              5-sulphonic acid                      "            "          NH              1-Aminonaphthalene-                                                                          "                                                              6-sulphonic acid                    1-(4'-Sulphophenyl)-                                                                         2-Methoxy-5-methyl-                                                                      NH              1-Aminonaphthalene-                                                                          red-brown            3-methyl-5-pyrazolone                                                                        aniline                    7-sulphonic acid                      "            "          NH              1-Phenylamino- "                                                              naphthalene-8-                                                                sulphonic acid                        "            "          NH              1-Carboxymethyl-                                                                             "                                                              aminonaphthalene-                                                             6-sulphonic acid                      "            "          NH              1-Carboxymethyl-                                                                             "                                                              amino-7-sulphonic                                                             acid                                  "            "          NH              2-Aminonaphthalene-                                                                          "                                                              6-sulphonic acid                      "            "          NH              2-Aminonaphthalene-                                                                          brown                                                          3,6-disulphonic acid                  "            "          NH              2-Aminonaphthalene-                                                                          "                                                              6,8-disulphonic acid                  "            "          NH              1-Hydroxynaphthalene-                                                                        red-                                                           4-sulphonic acid                                                                             violet                 "            "          NH              1-Hydroxynaphthalene-                                                                        "                                                              5-sulphonic acid                    1-(4'-Sulphophenyl)-                                                                         2-Methoxy-5-methyl-                                                                      NH              2-Hydroxynaphthalene-                                                                        red-                 3-methyl-5-pyrazolone                                                                        aniline                    6-sulphonic acid                                                                             violet                 "            "          NH              2-Hydroxynaphthalene-                                                                        "                                                              8-sulphonic acid                      "            "          NH              2-Hydroxynaphthalene-                                                                        "                                                              3,6-disulphonic acid                  "            "          NH              2-Hydroxynaphthalene-                                                                        "                                                              6,8-disulphonic acid                1-Hydroxynaphthalene-                                                                        "          NH              1-Amino-8-hydroxy-                                                                           blue                 4-sulphonic acid                          naphthalene-3,6-                                                              disulphonic acid                    1-Hydroxynaphthalene-                                                                        "          NH                "            "                    5-sulphonic acid                                                              1-Hydroxynaphthalene-                                                                        "          NH              1-Acetylamino-8-                                                                             "                    4-sulphonic acid                          hydroxynaphthalene-                                                           3,6-disulphonic acid                2-Amino-8-hydroxy-                                                                           "          NH              2-Hydroxynaphthalene-                                                                        "                    naphthalene-6-                            3,6-disulphonic acid                sulphonic acid                                                                2-Amino-8-hydroxy-                                                                           "          NH              2-Carboxymethylamino-                                                                        blue-                naphthalene-6-                            8-hydroxynaphthalene-                                                                        black                sulphonic acid                            6-sulphonic acid                    2-Amino-8-hydroxy-                                                                           2-Methoxy-5-                                                                             NH              2-Amino-8-hydroxy-                                                                           blue-                naphthalene-6- methylaniline              naphthalene-3,6-                                                                             black                sulphonic acid                            disulphonic acid                    2-Hydroxynaphthalene-                                                                        "          NH              1-Amino-8-hydroxy-                                                                           blue                 6,8-disulphonic acid                      naphthalene-4-                                                                sulphonic acid                        "            "          NH              1-Amino-8-hydroxy-                                                                           "                                                              naphthalene-3,6-                                                              disulphonic acid                    1-Phenyl-5-pyrazolone-                                                                       "          NH              1-Aminonaphthalene-                                                                          red-brown            3-carboxylic acid                         4-sulphonic acid                      "            "          NH              1-Aminonaphthalene-                                                                          "                                                              6-sulphonic acid                      "            "          NH              1-Hydroxynaphthalene-                                                                        red-                                                           4-sulphonic acid                                                                             violet                 "            "          NH              2-Hydroxynaphthalene-                                                                        "                                                              3,6-disulphonic acid                1-(4'-Sulphophenyl)-5-                                                                       "          NH              1-Phenylamino- brown                pyrazolone-3-carboxylic                   naphthalene-8-                      acid                                      sulphonic acid                        "            "          NH              1-Hydroxynaphthalene                                                                         red-                                                                          violet                 "            "          NH              2-Hydroxynaphthalene                                                                         "                    1-(4'-Sulphophenyl)-                                                                         2-Methoxy-5-methyl-                                                                       NH             2-Hydroxynaphthalene-                                                                        red-                 5-pyrazolone-3-                                                                              aniline                    3-carboxylic acid                                                                            violet               carboxylic acid                                                                 "            "          NH              1-Hydroxynaphthalene-                                                                        "                                                              4-sulphonic acid                    1-Hydroxynaphthalene                                                                         "          NH              Acetoacetic acid                                                                             orange-                                                        2,5-disulphoanilide                                                                          red                  2-Hydroxynaphthalene                                                                         "          NH              Acetoacetic acid                                                                             "                                                              2,5-disulphoanilide                 2-Hydroxynaphthalene-                                                                        "          NH              Acetoacetic acid                                                                             "                    3-carboxylic acid                         2,5-disulphoanilide                 1-(4'-Sulphophenyl)-                                                                         "          NH              2-Amino-8-hydroxy-                                                                           brown                3-methyl-5-pyrazolone                     naphthalene-6-                                                                sulphonic acid                      1-(2'-Sulphophenyl)-                                                                         "          NH                "            "                    3-methyl-5-pyrazolone                                                         1-(3'-Sulphophenyl)-                                                                         "          NH                "            "                    3-methyl-5-pyrazolone                                                         1-Phenyl-5-    "          NH                "            "                    pyrazolone-3-                                                                 carboxylic acid                                                               1-(4'-Sulphophenyl)-                                                                         2-Methoxy-5-methyl-                                                                      NH              2-Amino-8-hydroxy-                                                                           brown                5-pyrazolone-3-                                                                              aniline                    naphthalene-6-                      carboxylic acid                           sulphonic acid                        "            "          NH              2-Amino-5-hydroxy-                                                                           red-brown                                                      naphthalene-7-                                                                sulphonic acid                      1-(4'-Sulphophenyl)-                                                                         "          NH              2-Methylamino-8-                                                                             brown                3-methyl-5-                               hydroxynaphthalene-                 pyrazolone                                6-sulphonic acid                      "            "          NH              2-Dimethylamino-8-                                                                           "                                                              hydroxynaphthalene-                                                           6-sulphonic acid                      "            "          NH              2-Phenylamino-8-                                                                             "                                                              hydroxynaphthalene-                                                           6-sulphonic acid                      "            "          NH              2-Carboxymethylamino-                                                                        "                                                              8-hydroxynaphthalene-                                                         6-sulphonic acid                      "            "          NH              Acetoacetic acid                                                                             orange                                                         3-sulphoanilide                     1-Phenyl-5-pyrazolone-                                                                       2-Methoxy-5-methyl-                                                                      NH              Acetoacetic acid                                                                             orange               3-carboxylic acid                                                                            aniline                    3-sulphoanilide                     1-(4'-Sulphophenyl)-5-                                                                       "          NH                "            "                    pyrazolone-3-                                                                 carboxylic acid                                                                 "            "          NH              Aceotacetic acid                                                                             "                                                              anilide                             1-(2',5'-Dichloro-4'-                                                                        "          NH              Acetoacetic acid                                                                             "                    sulphophenyl)-3-                          3-sulphoanilide                     methyl-5-pyrazolone                                                           1-(2',4'-Disulpho-                                                                           "          NH              Acetoacetic acid                                                                             "                    phenyl)-3-methyl-5-                       anilide                             pyrazolone                                                                    1-(2',5'-Disulpho-                                                                           "          NH                "            "                    phenyl)-3-methyl-5-                                                           pyrazolone                                                                      "            "          NH              Acetoacetic acid                                                                             "                                                              2-methoxyanilide                    1-Phenyl-5-pyrazo-                                                                           "          NH              Acetoacetic acid                                                                             "                    lone-3-carboxylic                         2,5-disulphoanilide                 acid                                                                          1-Phenyl-5-pyrazolone-                                                                       2-Methoxy-5-methyl-                                                                       NH             1,3-Dihydroxybenzene-                                                                        red-brown            3-carboxylic acid                                                                            aniline                    4-sulphonic acid                      "            "          NH              3-Aminophenol-4-                                                                             "                                                              sulphonic acid                        "            "          NH              1,3-Diaminobenzene-                                                                          brown                                                          4-sulphonic acid                      "            "          NH              2,4-Diaminotoluene-                                                                          "                                                              5-sulphonic acid                    1-(4'-Sulphophenyl)-                                                                         "          NH              2-Hydroxybenzoic                                                                             orange               3-methyl-5-pyrazolone                                                           "            "          NH              3-Hydroxybenzene-                                                                            "                                                              sulphonic acid                        "            "          NH              1,3-Dihydroxybenzene-                                                                        orange-                                                        4-sulphonic acid                                                                             brown                  "            "          NH              3-Aminophenol-4-                                                                             "                                                              sulphonic acid                        "            "          NH              1,3-Diaminobenzene-                                                                          red-brown                                                      4-sulphonic acid                      "            "          NH              2,4-Diaminotoluene-                                                                          "                                                              5-sulphonic acid                    1-(4'-Sulphophenyl)-                                                                         2-Methoxy-5-methyl-                                                                      NH              3-Carboxymethylamino-                                                                        red-brown            3-methyl-5-pyrazolone                                                                        aniline                    phenol                                "            "          NH              1-Carboxymethylamino-                                                                        "                                                              3-aminobenzene                        "            "          NH              1,3-Biscarboxymethyl-                                                                        "                                                              aminobenzene                           "           "          NH              1-Carboxymethylamino-                                                                        "                                                              3-amino-4-methyl-                                                             benzene                             1-(4'-Sulphophenyl)-                                                                         "          NH              Phenol         orange-red           pyrazolone-3-carboxy-                                                         lic acid                                                                        "            "          NH              3-Aminophenol  red-brown              "            "          NH              1,3-Dihydroxybenzene                                                                         "                      "            "          NH              1,3-Diaminobenzene                                                                           brown                  "            "          NH              1,3-Diamino-4-methyl-                                                                        "                                                              benzene                               "            "          NH              1,4-Diamino-4- "                                                              methoxybenzene                        "            "          NH              1,3-Diamino-4-chloro-                                                                        "                                                              benzene                             1-(4'-Sulphophenyl)-                                                                         2-Methoxy-5-methyl-                                                                      NH              1-(2'-Sulphophenyl)-                                                                         orange               3-methyl-5-pyrazolone                                                                        aniline                    3-methyl-5-pyrazolone                 "            "          NH              1-(3'-Sulphophenyl)-                                                                         "                                                              3-methyl-5-pyrazolone                 "            "          NH              1-Phenyl-5-pyrazolone-                                                                       "                                                              3-carboxylic acid                     "            "          NH              1-(4'-Sulphophenyl)-                                                                         "                                                              5-pyrazolone-3-                                                               carboxylic acid                       "            "          NH              1-(4'-Sulphophenyl)-                                                                         "                                                              5-pyrazolone-3-                                                               carboxylic acid ethyl                                                         ester                                 "            "          NH              1-(4'-Sulphophenyl)-                                                                         "                                                              5-pyrazolone-3-                                                               carboxylic acid amide               1-(2',5'-Disulpho-                                                                           "          NH              1-Phenyl-3-methyl-5-                                                                         "                    phenyl)-3-methyl-5-                       pyrazolone                          pyrazolone                                                                      "            "          NH              3-Methyl-5-pyrazolone                                                                        "                    1-(4'-Sulphophenyl)-                                                                         "          NH              4-Methyl-6-hydroxy-                                                                          orange-              3-methyl-5-pyrazolone                     2-pyridone-3-  red                                                            sulphonic acid                      1-(4'-Sulphophenyl)-                                                                         2-Methoxy-5-methyl-                                                                      NH              1,4-Dimethyl-6-                                                                              orange-              3-methyl-5-pyrazolone                                                                        aniline                    hydroxy-2-pyridone-                                                                          red                                                            3-sulphonic acid                    1-(4'-Sulphophenyl)-                                                                         "          NH              4-Methyl-6-hydroxy-                                                                          "                    5-pyrazolone-3-                           2-pyridone-3-                       carboxylic acid                           sulphonic acid                      1-(2',5'-Disulpho-                                                                           "          NH                "            "                    phenyl)-3-methyl-5-                                                           pyrazolone                                                                      "            "          NH              4-Methyl-3-cyano-6-                                                                          "                                                              hydroxy-2-pyridone                    "            "          NH              1,4-Dimethyl-3-cyano-                                                                        "                                                              6-hydroxy-2-pyridone                1-Phenyl-5-pyrazolone-                                                                       "          NH              1-(4'-Sulphophenyl)-                                                                         "                    3-carboxylic acid                         3-methyl-5-pyrazolone               1-(4'-Sulphophenyl)-                                                                         "          NH              1-(4'-Sulphophenyl)-                                                                         "                    5-pyrazolone-3-                           3-methyl-5-pyrazolone               carboxylic acid                                                               4-Methyl-6-hydroxy-                                                                          "          NH              Acetoacetic acid                                                                             "                    2-pyridone-3-                             3-sulphoanilide                     sulphonic acid                                                                  "            "          NH              Acetoacetic acid                                                                             "                                                              2,5-disulphoanilide                 4-Methyl-3-sulpho-6-                                                                         2-Methoxy-5-methyl-                                                                      NH              1,3-Dihydroxybenzene-                                                                        red-brown            hydroxy-2-pyridone                                                                           aniline                    4-sulphonic acid                      "            "          NH              3-Aminophenol-4-                                                                             "                                                              sulphonic acid                        "            "          NH              1,3-Diaminobenzene-                                                                          "                                                              4-sulphonic acid                      "            "          NH              2,4-Diaminotoluene-                                                                          "                                                              5-sulphonic acid                      "            "          NH              1,3-Biscarboxymethyl-                                                                        "                                                              aminobenzene                          "            "          NH              1,3-Bissulphomethyl-                                                                         "                                                              aminobenzene                          "            "          NH              1,3-Biscarboxymethyl-                                                                        "                                                              amino-4-methylbenzene                 "            "          NH              1,3-Diaminobenzene-                                                                          "                                                              4,6-disulphonic acid                  "            "          NH              1-Aminonaphthalene-                                                                          brown                                                          4-sulphonic acid                      "            "          NH              1-Aminonaphthalene-                                                                          "                                                              6-sulphonic acid                    4-Methyl-3-sulpho-6-                                                                         2-Methoxy-5-methyl-                                                                      NH              1-Aminonaphthalene-                                                                          brown                hydroxy-2-pyridone                                                                           aniline                    7-sulphonic acid                      "            "          NH              1-Carboxymethylamino-                                                                        "                                                              naphthalene-6-                                                                sulphonic acid                        "            "          NH              1-Carboxymethylamino-                                                                        "                                                              naphthalene-7-                                                                sulphonic acid                        "            "          NH              2-Aminonaphthalene-                                                                          "                                                              3,6-disulphonic acid                  "            "          NH              2-Aminonaphthalene-                                                                          "                                                              6,8-disulphonic acid                  "            "          NH              1-Hydroxynaphthalene-                                                                        red-                                                           4-sulphonic acid                                                                             violet                 "            "          NH              1-Hydroxynaphthalene-                                                                        "                                                              5-sulphonic acid                    4-Methyl-6-hydroxy-                                                                          "          NH              2-Hydroxynaphthalene-                                                                        "                    2-pyridone-3-                             3,6-disulphonic acid                sulphonic acid                                                                  "            "          NH              2-Hydroxynaphthalene-                                                                        "                                                              6,8-disulphonic acid                4-Methyl-6-hydroxy-2-                                                                        2-Methoxy-5-methyl-                                                                      NH              2-Amino-8-hydroxy-                                                                           brown                pyridone-3-sulphonic                                                                         aniline                    naphthalene-6-                      acid                                      sulphonic acid                        "            "          NH              2-Amino-8-hydroxy-                                                                           "                                                              naphthalene-3,6-                                                              disulphonic acid                      "            "          NH              2-Carboxymethylamino-                                                                        "                                                              8-hydroxynaphthalene-                                                         6-sulphonic acid                      "            "          NH              1-Amino-8-hydroxy-                                                                           black-                                                         naphthalene-3,6-                                                                             green                                                          disulphonic acid                      "            "          NH              1-(2'-Sulphophenyl)-                                                                         orange-red                                                     3-methyl-5-pyrazolone                 "            "          NH              1-(3'-Sulphophenyl)-                                                                         "                                                              3-methyl-5-pyrazolone                 "            "          NH              1-(4'-Sulphophenyl)-                                                                         "                                                              3-methyl-5-pyrazolone               4-Methyl-6-hydroxy-                                                                          2-Methoxy-5-methyl-                                                                      NH              1-(4'-Sulphophenyl)-                                                                         orange-              2-pyridone-3-  aniline                    5-pyrazolone-3-                                                                              red                  sulphonic acid                            carboxylic acid                       "            "          NH              1-(2',4'-Disulpho-                                                                           "                                                              phenyl)-3-methyl-5-                                                           pyrazolone                            "            "          NH              1-(2',5'-Disulpho-                                                                           "                                                              phenyl)-3-methyl-5-                                                           pyrazolone                          1,4-Dimethyl-6-                                                                              "          NH              1,3-Diaminobenzene-                                                                          brown                hydroxy-2-pyridone-                       4-sulphonic acid                    3-sulphonic acid                                                                "            "          NH              2,4-Diaminotoluene-                                                                          "                                                              5-sulphonic acid                      "            "          NH              3-Aminophenol-4-                                                                             "                                                              sulphonic acid                        "            "          NH              1-Aminonaphthalene-                                                                          "                                                              6-sulphonic acid                      "            "          NH              1-Hydroxynaphthalene-                                                                        red-violet                                                     4-sulphonic acid                      "            "          NH              2-Hydroxynaphthalene-                                                                        "                                                              3,6-disulphonic acid                1,4-Dimethyl-6-                                                                              2-Methoxy-5-methyl-                                                                      NH              2-Amino-8-hydroxy-                                                                           brown                hydroxy-2-pyridone-                                                                          aniline                    naphthalene-6-                      3-sulphonic acid                          sulphonic acid                        "            "          NH              Acetoacetic acid                                                                             orange                                                         3-sulphoanilide                       "            "          NH              1-(4'-Sulphophenyl)-                                                                         orange-                                                        3-methyl-5-pyrazolone                                                                        red                  1-Hydroxynaphthalene-                                                                        2,5-Dimethylaniline                                                                      NH              1-Hydroxynaphthalene-                                                                        red-                 4-sulphonic acid                          4-sulphonic acid                                                                             violet               2-Hydroxynaphthalene-                                                                        "          NH              2-Hydroxynaphthalene-                                                                        "                    3,6-disulphonic acid                      3,6-disulphonic acid                2-Hydroxynaphthalene-                                                                        "          NH              2-Hydroxynaphthalene-                                                                        "                    6,8-disulphonic acid                      6,8-disulphonic acid                Acetoacetic acid                                                                             "          NH              2-Amino-8-hydroxy-                                                                           brown                3-sulphoanilide                           naphthalene-6-                                                                sulphonic acid                      1-(4'-Sulphophenyl)-                                                                         "          NH                "            "                    3-methyl-5-pyrazolone                                                         Acetoacetic acid                                                                             "          NH              Acetoacetic acid                                                                             yellow-              3-sulphoanilide                           3-sulphoanilide                                                                              orange               1-Hydroxynaphthalene-                                                                        2,5-Dimethoxy-                                                                           NH              1-Hydroxynaphthalene-                                                                        red-                 4-sulphonic acid                                                                             aniline                    4-sulphonic acid                                                                             violet               2-Hydroxynaphthalene-                                                                        2,5-Dimethoxy-                                                                           NH              2-Hydroxynaphthalene-                                                                        red-                 3,6-disulphonic acid                                                                         aniline                    3,6-disulphonic                                                                              violet               2-Hydroxynaphthalene-                                                                        "          NH              2-Hydroxynaphthalene-                                                                        "                    6,8-disulphonic acid                      6,8-disulphonic acid                Acetoacetic acid                                                                             "          NH              Acetoacetic acid                                                                             yellow-              3-sulphoanilide                           3-sulphoanilide                                                                              orange               1-(4'-Sulphophenyl)-                                                                         "          NH              2-Amino-8-hydroxy-                                                                           brown                3-methyl-5-pyrazolone                     naphthalene-6-                                                                sulphonic acid                      Acetoacetic acid                                                                             "          NH              2-Amino-8-hydroxy-                                                                           "                    3-sulphoanilide                           naphthalene-6-                                                                sulphonic acid                      1-Hydroxynaphthalene-                                                                        3-Methylaniline                                                                          NH              1-Hydroxynaphthalene-                                                                        red-                 4-sulphonic acid                          4-sulphonic acid                                                                             violet               2-Hydroxynaphthalene-                                                                        "          NH              2-Hydroxynaphthalene-                                                                        "                    3,6-disulphonic acid                      3,6-disulphonic acid                2-Hydroxynaphthalene-                                                                        "          NH              2-Hydroxynaphthalene-                                                                        "                    6,8-disulphonic acid                      6,8-disulphonic acid                Acetoacetic acid                                                                             "          NH              2-Amino-8-hydroxy-                                                                           brown                3-sulphoanilide                           naphthalene-6-                                                                sulphonic acid                      1-(4'-Sulphophenyl)-                                                                         "          NH              "              "                    3-methyl-5-pyrazolone                                                         Acetoacetic acid                                                                             3-Methylaniline                                                                          NH              Acetoacetic acid                                                                             yellow-              3-sulphoanilide                           3-sulphoanilide                                                                              orange               1-Hydroxynaphthalene-                                                                        3-Methoxyaniline                                                                         NH              1-Hydroxynaphthalene-                                                                        red-                 4-sulphonic acid                          4-sulphonic acid                                                                             violet               2-Hydroxynaphthalene-                                                                        "          NH              2-Hydroxynaphthalene-                                                                        "                    3,6-disulphonic acid                      3,6-disulphonic acid                2-Hydroxynaphthalene-                                                                        "          NH              2-Hydroxynaphthalene-                                                                        "                    6,8-disulphonic acid                      6,8-disulphonic acid                Acetoacetic acid                                                                             "          NH              Acetoacetic acid                                                                             yellow-              3-sulphoanilide                           3-sulphoanilide                                                                              orange               1-(4'-Sulphophenyl)-                                                                         "          NH              2-Amino-8-hydroxy-                                                                           brown                3-methyl-5-pyrazolone                     naphthalene-6-                                                                sulphonic acid                      Acetoacetic acid                                                                             "          NH              2-Amino-8-hydroxy-                                                                           brown                3-sulphoanilide                           naphthalene-6-                                                                sulphonic acid                      1-Hydroxynaphthalene-                                                                        2-Ethoxy-5-methyl-                                                                       NH              1-Hydroxynaphthalene-                                                                        red-                 4-sulphonic acid                                                                             aniline                    4-sulphonic acid                                                                             violet               2-Hydroxynaphthalene-                                                                        "          NH              2-Hydroxynaphthalene-                                                                        "                    3,6-disulphonic acid                      3,6-disulphonic acid                2-Hydroxynaphthalene-                                                                        "          NH              2-Hydroxynaphthalene-                                                                        "                    6,8-disulphonic acid                      6,8-disulphonic acid                Acetoacetic acid                                                                             2-Ethoxy-5-methyl-                                                                       NH              2-Amino-8-hydroxy-                                                                           brown                3-sulphoanilide                                                                              aniline                    naphthalene-6-                                                                sulphonic acid                      1-(4'-Sulphophenyl)-3-                                                                       "          NH                "            brown                methyl-5-pyrazolone                                                           Acetoacetic acid                                                                             "          NH              Acetoacetic acid                                                                             yellow-              3-sulphoanilide                           3-sulphoanilide                                                                              orange               1-Hydroxynaphthalene-                                                                        3-Aminophenol                                                                            NH              1-Hydroxynaphthalene-                                                                        red-                 4-sulphonic acid                          4-sulphonic acid                                                                             violet               2-Hydroxynaphthalene-                                                                        "          NH              2-Hydroxynaphthalene-                                                                        "                    3,6-disulphonic acid                      3,6-disulphonic acid                2-Hydroxynaphthalene-                                                                        "          NH              2-Hydroxynaphthalene-                                                                        "                    6,8-disulphonic acid                      6,8-disulphonic acid                Acetoacetic acid                                                                             "          NH              Acetoacetic acid                                                                             yellow-              3-sulphoanilide                           3-sulphoanilide                                                                              orange               1-(4'-sulphophenyl)-                                                                         "          NH              2-Amino-8-hydroxy-                                                                           brown                3-methyl-5-pyrazolone                     naphthalene-6-                                                                sulphonic acid                      Acetoacetic acid                                                                             "          NH              2-Amino-8-hydroxy-                                                                           "                    3-sulphoanilide                           naphthalene-6-                                                                sulphonic acid                      1-Hydroxynaphthalene-                                                                        1-Amino-3-acetyl-                                                                        NH              1-Hydroxynaphthalene-                                                                        red-                 4-sulphonic acid                                                                             aminobenzene               4-sulphonic acid                                                                             violet               2-Hydroxynaphthalene-                                                                        "          NH              2-Hydroxynaphthalene-                                                                        "                    3,6-disulphonic acid                      3,6-disulphonic acid                2-Hydroxynaphthalene-                                                                        "          NH              2-Hydroxynaphthalene-                                                                        "                    6,8-disulphonic acid                      6,8-disulphonic acid                Acetoacetic acid                                                                             "          NH              2-Amino-8-hydroxy-                                                                           brown                3-sulphoanilide                           naphthalene-6-                                                                sulphonic acid                      1-(4'-Sulphophenyl)-                                                                         "          NH                "            "                    3-methyl-5-pyrazolone                                                         Acetoacetic acid                                                                             "          NH              Acetoacetic acid                                                                             yellow-              3-sulphoanilide                           3-sulphoanilide                                                                              orange               1-Hydroxynaphthalene-                                                                        1-Amino-3-acetyl-                                                                        NH              1-Hydroxynaphthalene-                                                                        red-                 4-sulphonic acid                                                                             amino-6-methyl-            4-sulphonic acid                                                                             violet                              benzene                                                        2-Hydroxynaphthalene-                                                                        "          NH              2-Hydroxynaphthalene-                                                                        "                    3,6-disulphonic acid                      3,6-disulphonic acid                2-Hydroxynaphthalene-                                                                        "          NH              2-Hydroxynaphthalene-                                                                        "                    6,8-disulphonic acid                      6,8-disulphonic acid                Acetoacetic acid                                                                             "          NH              Acetoacetic acid                                                                             yellow-              3-sulphoanilide                           3-sulphoanilide                                                                              orange               1-(4'-Sulphophenyl)-                                                                         1-Amino-3-acetyl-                                                                        NH              2-Amino-8-hydroxy-                                                                           brown                3-methyl-5-pyrazolone                                                                        amino-6-methyl-            naphthalene-6-                                     benzene                    sulphonic acid                      Acetoacetic acid                                                                             "          NH                "            "                    3-sulphoanilide                                                               1-Hydroxynaphthalene-                                                                        1-Amino-3-oxalyl-                                                                        NH              1-Hydroxynaphthalene-                                                                        red-                 4-sulphonic acid                                                                             aminobenzene               4-sulphonic acid                                                                             violet               2-Hydroxynaphthalene-                                                                        "          NH              2-Hydroxynaphthalene-                                                                        "                    3,6-disulphonic acid                      3,6-disulphonic acid                2-Hydroxynaphthalene-                                                                        "          NH              2-Hydroxynaphthalene-                                                                        "                    6,8-disulphonic acid                      6,8-disulphonic acid                Acetoacetic acid                                                                             "          NH              2-Amino-8-hydroxy-                                                                           brown                3-sulphoanilide                           naphthalene-6-                                                                sulphonic acid                      1-(4'-Sulphophenyl)-                                                                         "          NH                "            "                    3-methyl-5-pyrazolone                                                         Acetoacetic acid                                                                             "          NH              Acetoacetic acid                                                                             yellow-              3-sulphoanilide                           3-sulphoanilide                                                                              orange               1-Hydroxynaphthalene-                                                                        1-Amino-3-oxalyl-                                                                        NH              1-Hydroxynaphthalene-                                                                        red-                 4-sulphonic acid                                                                             amino-6-methyl-            4-sulphonic acid                                                                             violet                              benzene                                                        2-Hydroxynaphthalene-                                                                        1-Amino-3-oxalyl-                                                                        NH              2-Hydroxynaphthalene-                                                                        red-                 3,6-disulphonic acid                                                                         amino-6-methyl-            3,6-disulphonic                                                                              violet                              benzene                                                        2-Hydroxynaphthalene-                                                                        "          NH              2-Hydroxynaphthalene-                                                                        "                    6,8-disulphonic acid                      6,8-disulphonic acid                Acetoacetic acid                                                                             "          NH              Acetoacetic acid                                                                             yellow-              3-sulphoanilide                           3-sulphoanilide                                                                              orange               1-(4'-Sulphophenyl)-                                                                         "          NH              2-Amino-8-hydroxy-                                                                           brown                3-methyl-5-pyrazolone                     naphthalene-6-                                                                sulphonic acid                      Acetoacetic acid                                                                             "          NH              2-Amino-8-hydroxy-                                                                           brown                3-sulphoanilide                           naphthalene-6-                                                                sulphonic acid                      1-Hydroxynaphthalene-                                                                        1-Amino-3-acetyl-                                                                        NH              1-Hydroxynaphthalene-                                                                        red                  4-sulphonic acid                                                                             amino-6-methoxy-           4-sulphonic acid                                                                             violet                              benzene                                                        2-Hydroxynaphthalene-                                                                        "          NH              2-Hydroxynaphthalene-                                                                        "                    3,6-disulphonic acid                      3,6-disulphonic acid                2-Hydroxynaphthalene-                                                                        "          NH              2-Hydroxynaphthalene-                                                                        "                    6,8-disulphonic acid                      6,8-disulphonic acid                Acetoacetic acid                                                                             "          NH              2-Amino-8-hydroxy-                                                                           brown                3-sulphoanilide                           naphthalene-6-                                                                sulphonic acid                      1-(4'-Sulphophenyl)-                                                                         1-Amino-3-acetyl-                                                                        NH              2-Amino-8-hydroxy-                                                                           brown                3-methyl-5-pyrazolone                                                                        amino-6-methoxy-           naphthalene-6-                                     benzene                    sulphonic acid                      Acetoacetic acid                                                                             "          NH              Acetoacetic acid                                                                             yellow-              3-sulphoanilide                           3-sulphoanilide                                                                              orange               1-Hydroxynaphthalene-                                                                        1-Amino-3-acetyl-                                                                        NH              1-Hydroxynaphthalene-                                                                        red-                 4-sulphonic acid                                                                             amino-6-ethoxy-            4-sulphonic acid                                                                             violet                              benzene                                                        2-Hydroxynaphthalene-                                                                        "          NH              2-Hydroxynaphthalene-                                                                        "                    3,6-disulphonic acid                      3,6-disulphonic acid                2-Hydroxynaphthalene-                                                                        "          NH              2-Hydroxynaphthalene-                                                                        "                    6,8-disulphonic acid                      6,8-disulphonic acid                Acetoacetic acid                                                                             "          NH              Acetoacetic acid                                                                             yellow-              3-sulphoanilide                           3-sulphoanilide                                                                              orange               1-(4'-Sulphophenyl)-                                                                         "          NH              2-Amino-8-hydroxy-                                                                           brown                3-methyl-5-pyrazolone                     naphthalene-6-                                                                sulphonic acid                      Acetoacetic acid                                                                             "          NH                "            "                    3-sulphoanilide                                                               1-Hydroxynaphthalene-                                                                        2-Methoxy-5-chloro-                                                                      NH              1-Hydroxynaphthalene-                                                                        red-                 4-sulphonic acid                                                                             aniline                    4-sulphonic acid                                                                             violet               2-Hydroxynaphthalene-                                                                        "          NH              2-Hydroxynaphthalene-                                                                        "                    3,6-disulphonic acid                      3,6-disulphonic acid                2-Hydroxynaphthalene-                                                                        "          NH              2-Hydroxynaphthalene-                                                                        "                    6,8-disulphonic acid                      6,8-disulphonic acid                Acetoacetic acid                                                                             "          NH              2-Amino-8-hydroxy-                                                                           brown                3-sulphoanilide                           naphthalene-6-                                                                sulphonic acid                      1-(4'-Sulphophenyl)-                                                                         "          NH              "              "                    3-methyl-5-pyrazolone                                                         Acetoacetic acid                                                                             "          NH              Acetoacetic acid                                                                             yellow-              3-sulphoanilide                           3-sulphoanilide                                                                              orange               2-Amino-8-hydroxy-                                                                           1-Amino-3-oxalyl-                                                                        NH              2-Amino-8-hydroxy-                                                                           black-               naphthalene-6- aminobenzene               naphthalene-6- blue                 sulphonic acid                            sulphonic acid                        "            1-Amino-3-oxalyl-                                                                        NH              "              "                                   amino-6-methyl-                                                               benzene                                                        2-Hydroxynaphthalene-                                                                        1-Amino-3-oxalyl-                                                                        NH              1,3-Diaminobenzene                                                                           violet               3,6-disulphonic acid                                                                         aminobenzene                                                   1,3-Dihydroxybenzene                                                                         "          NH              1,3-Dihydroxybenzene                                                                         red                  1-Hydroxynaphthalene-                                                                        1-Amino-3-oxalyl-                                                                        NH              2-Hydroxynaphthalene                                                                         violet               4-sulphonic acid                                                                             aminobenzene                                                   1-(4'-Sulphophenyl)-                                                                         Aniline    NH              1-(4'-Sulphophenyl)-                                                                         orange               3-methyl-5-pyrazolone                     3-methyl-5-pyrazolone               2-Hydroxybenzoic acid                                                                        "          NH              2-Amino-8-hydroxy-                                                                           brown                                                          naphthalene-6-                                                                sulphonic acid                        "            "          NH              2-Carboxymethylamino-                                                                        "                                                              8-hydroxynaphthalene-                                                         6-sulphonic acid                    1-Amino-8-hydroxy-                                                                           "          NH              1-Amino-8-hydroxy-                                                                           blue                 naphthalene-3,6-                          naphthalene-3,6-                    disulphonic acid                          disulphonic acid                      "            "          NH              2-Amino-8-hydroxy-                                                                           "                                                              naphthalene-6-                                                                sulphonic acid                      1-(4'-Sulphophenyl)-                                                                         2-Aminotoluene                                                                           NH              1-(4'-Sulphophenyl)-                                                                         orange               3-methyl-5-pyrazolone                     3-methyl-5-pyrazolone               2-Hydroxybenzoic acid                                                                        "          NH              2-Amino-8-hydroxy-                                                                           brown                                                          naphthalene-6-                                                                sulphonic acid                      2-Hydroxybenzoic acid                                                                        2-Aminotoluene                                                                           NH              2-Carboxymethylamino-                                                                        brown                                                          8-hydroxynaphthalene-                                                         6-sulphonic acid                    1-Amino-8-hydroxy-                                                                           "          NH              1-Amino-8-hydroxy-                                                                           blue                 naphthalene-3,6-                          naphthalene-3,6-                    disulphonic acid                          disulphonic acid                      "            "          NH              2-Amino-8-hydroxy-                                                                           blue                                                           naphthalene-6-                                                                sulphonic acid                      1-(4'-Sulphophenyl)-                                                                         2-Methoxyaniline                                                                         NH              1-(4'-Sulphophenyl)-                                                                         orange               3-methyl-5-pyrazolone                     3-methyl-5-pyrazolone               2-Hydrobenzoic acid                                                                          "          NH              2-Amino-8-hydroxy-                                                                           brown                                                          naphthalene-6-                                                                sulphonic acid                        "            "          NH              2-Carboxymethylamino-                                                                        brown                                                          8-hydroxynaphthalene-                                                         6-sulphonic acid                    1-Amino-8-hydroxy-                                                                           "          NH              1-Amino-8-hydroxy-                                                                           blue                 naphthalene-3,6-                          naphthalene-3,6-                    disulphonic acid                          disulphonic acid                    1-Amino-8-hydroxy-                                                                           2-Methoxyaniline                                                                         NH              2-Amino-8-hydroxy-                                                                           blue                 naphthalene-3,6-                          naphthalene-6-                      disulphonic acid                          sulphonic acid                      1-(4'-Sulphophenyl)-                                                                         2-Ethoxyaniline                                                                          NH              1-(4'-Sulphophenyl)-                                                                         orange               3-methyl-5-pyrazolone                     3-methyl-5-pyrazolone               2-Hydroxybenzoic acid                                                                        "          NH              2-Amino-8-hydroxy-                                                                           brown                                                          naphthalene-6-sulphonic                                                       acid                                  "            "          NH              2-Carboxymethylamino-                                                                        brown                                                          8-hydroxynaphthalene-                                                         6-sulphonic acid                    1-Amino-8-hydroxy-                                                                           "          NH              1-Amino-8-hydroxy-                                                                           blue                 naphthalene-3,6-                          naphthalene-3,6-                    disulphonic acid                          disulphonic acid                      "            "          NH              2-Amino-8-hydroxy-                                                                           blue                                                           naphthalene-6-                                                                sulphonic acid                      1-(4'-Sulphophenyl)-                                                                         2-Chloroaniline                                                                          NH              1-(4'-Sulphophenyl)-                                                                         orange               3-methyl-5-pyrazolone                     3-methyl-5-pyrazolone               2-Hydroxybenzoic acid                                                                        "          NH              2-Amino-8-hydroxy-                                                                           brown                                                          naphthalene-6-                                                                sulphonic acid                      2-Hydroxybenzoic                                                                             2-Chloroaniline                                                                          NH              2-Carboxymethylamino-                                                                        brown                acid                                      8-hydroxynaphthalene-                                                         6-sulphonic acid                    1-Amino-8-hydroxy-                                                                           "          NH              1-Amino-8-hydroxy-                                                                           blue                 naphthalene-3,6-                          naphthalene-3,6-                    disulphonic acid                          disulphonic acid                      "            "          NH              2-Amino-8-hydroxy-                                                                           "                                                              naphthalene-6-                                                                sulphonic acid                      1-(4'-Sulphophenyl)-                                                                         3-Chloroaniline                                                                          NH              1-(4'-Sulphopenyl)-                                                                          orange               3-methyl-5-pyrazolone                     3-methyl-5-pyrazolone               2-Hydroxybenzoic acid                                                                        "          NH              2-Amino-8-hydroxy-                                                                           brown                                                          naphthalene-6-                                                                sulphonic acid                        "            "          NH              2-Carboxymethylamino-                                                                        brown                                                          8-hydroxynaphthalene-                                                         6-sulphonic acid                    1-Amino-8-hydroxy-                                                                           "          NH              1-Amino-8-hydroxy-                                                                           blue                 naphthalene-3,6-                          naphthalene-3,6-                    disulphonic acid                          disulphonic acid                      "            "          NH              2-Amino-8-hydroxy-                                                                           blue                                                           naphthalene-6-                                                                sulphonic acid                      1-Amino-8-hydroxy-                                                                           2-Methoxy-5-methyl-                                                                      O               1-Amino-8-hydroxy-                                                                           blue                 naphthalene-3,6-                                                                             aniline                    naphthalene-3,6-                    disulphonic acid                          disulphonic acid                      "            "          S                 "            "                      "            "          S, 6-CH.sub.3     "            "                      "            "          N(CH.sub.3)       "            "                      "            "          N(C.sub.6 H.sub.5)                                                                              "            "                      "            "          NH, 4-CH.sub.3    "            "                      "            "          NH, 7-Cl          "            "                      "            "          NH, 2'-CH.sub.3   "            "                      "            "          NH,3'-CH.sub.3    "            "                      "            "          NH, 2'-Cl         "            "                      "            "          NH, 3'-Cl         "            "                      "            "          NH, 7-Cl, 3'-Cl   "            "                    __________________________________________________________________________

                                      Table II                                    __________________________________________________________________________     Coupling component                                                                       coupling componentDiazotisable                                                           ##STR36##        Coupling component                                                                         shade onColour             B.sub.1H   MNH.sub.2                                                                              X                  B.sub.2H   cotton                    __________________________________________________________________________    2-Hydroxybenzoic                                                                         2-Methoxy-5-methyl-                                                                      O                2-Amino-8-hydroxy-                                                                         brown                     acid       aniline                     naphthalene-6-                                                                sulphonic acid                         2-Hydroxybenzoic                                                                         2-Methoxy-5-methyl-                                                                      O                2-Carboxymethylamino-                                                                      brown                     acid       aniline                     naphthalene-6-                                                                sulphonic acid                         1-Amino-8-hydroxy-                                                                       2-Methoxy-5-methyl-                                                                      O                1-Amino-8-hydroxy-                                                                         blue                      naphthalene-3,6-                                                                         aniline                     naphthalene-3,6-                       disulphonic acid                       disulphonic acid                       1-Amino-8-hydroxy-                                                                       2-Methoxy-5-methyl-                                                                      S                1-Amino-8-hydroxy-                                                                         blue                      naphthalene-3,6-                                                                         aniline                     naphthalene-3,6-                       disulphonic acid                       disulphonic acid                       1-(4'-Sulphophenyl)-                                                                     2-Methoxy-5-methyl-                                                                      S                1-(4'-Sulphophenyl)-                                                                       orange                    3-methyl-5-pyrazolone                  3-methyl-5-pyrazolone                  __________________________________________________________________________

We claim:
 1. A water soluble trisazo dyestuff of the formula

    B.sub.1 -N═N-Z-N═N-M-N═N-B.sub.2

wherein M is ##STR37## B₁ and B₂ are the same or different and areselected from the group consisting of ##STR38## 2.4-dihydroxy-3-quinolyl and 2,6-diamino-5-pyridyl;Z is ##STR39## X is##STR40## --O-- or --S--; R₁ is hydrogen, alkyl having 1 to 4 carbonatoms, phenyl or benzyl; R₃ is hydrogen, chloro or alkyl or alkoxyhaving 1 to 4 carbon atoms; R₄ is hydrogen chloro, alkyl or alkoxyhaving 1 to 4 carbon atoms, hydroxy, alkanoylamino having 1 to 4 carbonatoms, benzoylamino, naphthoylamino, oxalylamino, carboxyalkylaminohaving 2 to 5 carbon atoms, sulphoalkylamino having 1 to 4 carbon atomsor oxyalkylamino having 1 to 4 carbon atoms; R₅ is hydrogen or alkylhaving 1 to 8 carbon atoms; R₆ is --CN, --COOH, --CONH₂ or --SO₃ H; R₇is hydrogen or alkyl having 1 to 4 carbon atoms; R₈ is hydrogen, phenylor phenyl substituted with a methyl, nitro, chloro or sulpho; R₉ ismethyl, carboxyl or alkoxycarbonyl having 2 to 5 carbon atoms; R₁₀ ishydrogen, methyl, methoxy, chloro, --COOH or --SO₃ H; E is a hydroxyl,amino, alkylamino having 1 to 4 carbon atoms, phenylamino,naphthylamino, benzoylamino, naphthoylamino, alkanoylamino having 2 to 5carbon atoms, carboxyalkylamino having 2 to 5 carbon atoms,sulphoalkylamino having 1 to 4 carbon atoms, hydroxyalkylamino having 1to 4 carbon atoms or dialkylamino having 1 to 4 carbon atoms in eachalkyl; E' is hydrogen or the same or a different member of the group ofsubstituents standing for E, R₁₁, r₁₂ and R₁₃ are alkyl or alkoxy having1 to 4 carbon atoms, carboxyl, sulpho, chloro, bromo, nitro ormethoxycarbonyl; R₁₄ and R₁₅ are hydrogen, methyl, ethyl, methoxy,ethoxy or chloro; with the proviso that at least one of M, B₁ and B₂includes a sulpho substituent.
 2. A water soluble trisazo dyestuff ofclaim 1 wherein B₁, B₂ or both is ##STR41##
 3. A water soluble trisazodyestuff of claim 1 wherein B₁, B₂ or both is ##STR42##
 4. A watersoluble trisazo dyestuff of claim 1 wherein B₁, B₂ or both is ##STR43##5. A water soluble trisazo dyestuff of the formula

    B.sub.1 -N═N-Z-N═N-M-N═N-B.sub.2

wherein M is ##STR44## B₁ and B₂ are the same or different and areselected from the group consisting of ##STR45## Z is selected from thegroup consisting of ##STR46## X is ##STR47## --O-- or --S--; R₁ ishydrogen, alkyl having 1 to 4 carbon atoms, phenyl or benzyl; R₃ ishydrogen, chloro or alkyl or alkoxy having 1 to 4 carbon atoms; R₄ ishydrogen chloro, alkyl or alkoxy having 1 to 4 carbon atoms, hydroxy,alkanoylamino having 1 to 4 carbon atoms, benzoylamino, naphthoylamino,oxalylamino, carboxyalkylamino having 2 to 5 carbon atoms,sulphoalkylamino having 1 to 4 carbon atoms or oxyalkylamino having 1 to4 carbon atoms; E is a hydroxyl, amino, alkylamino having 1 to 4 carbonatoms, phenylamino, naphthylamino, benzoylamino, naphthoylamino,alkanoylamino having 2 to 5 carbon atoms, carboxyalkylamino having 2 to5 carbon atoms, sulphoalkylamino having 1 to 4 carbon atoms,hydroxyalkylamino having 1 to 4 carbon atoms or dialkylamino having 1 to4 carbon atoms in each alkyl; E' is hydrogen or the same or a differentmember of the group of substituents standing for E; R₁₁, r₁₂ and R₁₃ arealkyl or alkoxy having 1 to 4 carbon atoms, carboxyl, sulpho, chloro,bromo, nitro or methoxycarbonyl; R₁₄ and R₁₅ are hydrogen, methyl,ethyl, methoxy, ethoxy or chloro; with the proviso that at least one ofM, B₁ and B₂ includes a sulpho substituent.
 6. A water soluble trisazodyestuff of claim 5 wherein B₁, B₂ or both is ##STR48##
 7. A watersoluble trisazo dyestuff of claim 5 wherein B₁, B₂ or both is ##STR49##8. A water soluble trisazo dyestuff of claim 5 wherein X is ##STR50## 9.A water soluble trisazo dyestuff of claim 5 wherein R₁₄ and R₁₅ are thesame or different and are selected from the group consisting ofhydrogen, chloro and methyl.
 10. A water soluble trisazo dyestuff ofclaim 5 having from 2-4 sulpho substituents.
 11. A water soluble trisazodyestuff according to claim 5 having the formula ##STR51##
 12. A watersoluble trisazo dyestuff according to claim 5 having the formula##STR52##
 13. A water soluble trisazo dyestuff according to claim 5having the formula ##STR53##